CN1916097A - Adhesive sheet and semiconductor device and process for producing the same - Google Patents

Adhesive sheet and semiconductor device and process for producing the same Download PDF

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Publication number
CN1916097A
CN1916097A CNA2006101002870A CN200610100287A CN1916097A CN 1916097 A CN1916097 A CN 1916097A CN A2006101002870 A CNA2006101002870 A CN A2006101002870A CN 200610100287 A CN200610100287 A CN 200610100287A CN 1916097 A CN1916097 A CN 1916097A
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adhesive sheet
equal
radiation exposure
pressure sensitive
mentioned
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CN1916097B (en
Inventor
川上广幸
稻田祯一
增子崇
大久保惠介
畠山惠一
柳川俊之
加藤木茂树
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/27—Manufacturing methods
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/30—Technical effects
    • H01L2924/35—Mechanical effects
    • H01L2924/351—Thermal stress

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  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

An adhesive sheet comprising a pressure-sensitive adhesive layer and a substrate layer, wherein the strength of adhesion between the pressure-sensitive adhesive layer and the substrate layer is controlled by means of irradiation with a radiation and the pressure-sensitive adhesive layer comprises the following ingredients: (a) a thermoplastic resin, (b) a heat-polymerizable ingredient, and (c) a compound which generates a base upon irradiation with the radiation. The adhesive sheet satisfies the following inconsistent requirements: it should have tackiness sufficient to keep semiconductor elements held thereon during dicing and, upon subsequent irradiation with a radiation for regulating the strength of adhesion between the pressure-sensitive adhesive layer and the substrate, come to have such low tackiness that it does not damage the elements during pickup.

Description

Adhesive sheet and semiconductor device and manufacture method thereof
The application is that international application no is PCT/JP02/08616, and national applications number is 02816650.7, and the applying date is on August 27th, 2002, and denomination of invention is divided an application for the patent application of " adhesive sheet and semiconductor device and manufacture method thereof ".
Technical field
The invention relates to adhesive sheet, use the semiconductor device and the manufacture method thereof of this adhesive sheet.
Background technology
In the past, supported with the main silver paste that uses in the joint of support member at semiconductor element and semiconductor element.But miniaturization, high performance along with in recent years semiconductor element also require its miniaturization, fine and closely wovenization to employed support member.For such requirement, because because of overflowing or the difficulty of the control of the thickness of bad generation during wire-bonded that the inclination of semiconductor element causes, binder layer, and the generation in the space of binder layer etc., silver paste can not adapt to above-mentioned requirements.
Therefore, in order to adapt to above-mentioned requirements, used the tackiness agent of film like in recent years.
This film like tackiness agent uses in the adhesion mode inside monolithic adheres to mode or wafer.Person's the monolithic film like tackiness agent that adheres to mode is made the occasion of semiconductor device before use, after the adhesive film of roll coil of strip shape is downcut (cutting) or stamping-out (punching) and is cut into monolithic, this monolithic is bonded on the support member; On the adherent support member of above-mentioned band film like tackiness agent, engage by cutting (dicing) operation the semiconductor element of singualtion, the support member of making the band semiconductor element again; Then as required, through wire-bonded operation, sealing process etc., obtain semiconductor device.But,,, therefore compare the problem that exists manufacturing cost to increase with the method for using silver paste so need cut out adhesive film and be bonded in the assembling device of the special use on the support member because use above-mentioned monolithic to adhere to the film like tackiness agent of mode.
On the other hand, the film like tackiness agent that adheres to mode in the wafer the inside of using the latter is made the occasion of semiconductor device, at first at the inside of semiconductor wafer adhering film shape tackiness agent, again at the another side applying dicing tape (dicing tape) of film like tackiness agent; From above-mentioned wafer, semiconductor element is cut into a plurality of monolithics then; Take out the one semiconductor element that has the film like tackiness agent, it is combined on the support member; Heating, curing, wire-bonded operation through after this obtain semiconductor device.The film like tackiness agent that this wafer the inside adheres to mode will be combined in the semiconductor element of film like tackiness agent on the support member, therefore do not need to make the device of film like tackiness agent singualtion, the part that can directly use the assembling device that silver paste in the past uses or will add the device of hot plate etc. is improved and is used.Therefore, in the assembly method of using the film like tackiness agent, it is suppressed to cheaper method as manufacturing cost, just comes on the scene.
With the dicing tape that the film like tackiness agent that adheres to mode inside this wafer uses together, roughly divide into pressure-sensitive type and UV (ultraviolet ray) type dicing tape.
The former pressure-sensitive type dicing tape, normally coating adhesive forms on the substrate film of polyvinyl chloride or polyolefin.To this dicing tape, both required it to have enough high adhesions, so that during the cut-out in cutting action, each element is unlikely in the rotation of incised layer disperses, also require it to have the low bounding force of the degree of can taking out, so that tackiness agent is non-cohesive on each element when taking out, and lesion element not., because there is not fully to have concurrently the pressure-sensitive type dicing tape of above-mentioned opposite two kinds of performances, so the operation that all will change dicing tape corresponding to the size or the processing conditions of every kind of semiconductor element.In addition, be necessary owing to have the various dicing tapes of the various bounding forces that satisfy size of component or processing conditions, so the material requirements planning of dicing tape is complicated.Have, in recent years, especially CPU, storer make semiconductor element to large scale development to the result that high capacity develops, and the storer forward slimming of using in goods such as IC-card or storage card development again.Maximization or slimming along with these semiconductor elements, above-mentioned pressure-sensitive type dicing tape, because the bond strength height when taking out, therefore problem such as generating device fracture when taking out, the bed knife (high adhesion) in the time of can not having satisfied cutting and the such cross-demand mutually of peeling force (hanging down bounding force) when taking out.
On the other hand, the latter's UV type dicing tape though have high adhesion when cutting, before taking out, becomes low bounding force through ultraviolet ray (UV) irradiation.Therefore, improve by the problem that above-mentioned pressure-sensitive type adhesive tape is had, it can be widely used as dicing tape.
By using this UV type dicing tape, though the problem of above-mentioned pressure-sensitive type dicing tape gets improvement to a certain degree, but still insufficient, and concerning the film like tackiness agent of wafer the inside adhesion mode, also have the further problem of improvement that remains.That is, under the situation of using the method for the film like tackiness agent of adhesion mode inside the wafer, even, need such two of adhered film shape tackiness agent and dicing tape to attach operations at above-mentioned cutting action.And the adhesive transfer that has a dicing tape to the film like tackiness agent, problem such as binding property reduction.Therefore, the adhesive sheet that has the function of film like tackiness agent and dicing tape in the time of will seeking common ground, but, also do not have to such an extent that be and both have enough high adhesions, disperse so that semiconductor element is unlikely when cutting, has low bounding force again, so that each element can the such adhesive sheet that satisfies the phase cross-demand of damaged when taking out.
From as can be known above, seeking a kind of adhesive sheet always, it plays a role as dicing tape in cutting action, plays a role as the good adhesive sheet of joint reliability in the joint operation of semiconductor element and support member.In addition, also seeking a kind of adhesive sheet, desired thermotolerance and wet fastness and operation were good when it had on semiconductor element supports with support member the big semiconductor element of the difference of encapsulation thermal expansivity always.In addition, also seeking to make the manufacture method of the semiconductor device that manufacturing process oversimplifies always.
Summary of the invention
To this, present inventors are from found that the composition aspect of adhesive sheet is studied, the adhesive sheet with the pressure sensitive adhesive layer that contains special component can address the above problem.Present inventors study the back discovery for to seek the operation of above-mentioned adhesive sheet and the raising of reliability from characteristic aspect and chemical aspect in addition, and the adhesive sheet with particular characteristics can further obtain the raising of operation and reliability.
That is, the invention relates to the adhesive sheet that possesses the binder layer that contains special component.
＜1〉adhesive sheet, it has pressure sensitive adhesive layer and substrate layer, and the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, and above-mentioned pressure sensitive adhesive layer contains following composition:
(a) thermoplastic resin,
(b) thermopolymerization composition, and
(c) produce the compound of base through radiation exposure.
In addition, the present invention also is about having the adhesive sheet of following parameter.
＜2〉above-mentioned adhesive sheet, wherein, above-mentioned pressure sensitive adhesive layer is that the bond strength at preceding above-mentioned pressure sensitive adhesive layer of (A1) radiation exposure and above-mentioned substrate layer interface is more than or equal to 200mN/cm, perhaps (A2) adhesion strength of 25 ℃ utilizing the above-mentioned pressure sensitive adhesive layer before the radiation exposure of  5.1mm probe assay is for more than or equal to 0.5N, and this adhesive sheet has at least one characteristic in the following characteristic:
(B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m,
(B2) melt viscosity during 160 ℃ before the radiation exposure is 50～100000Pas.
In addition, the present invention is still about having the adhesive sheet of following parameter.
＜3〉adhesive sheet, it bounding force that possesses between pressure sensitive adhesive layer and substrate layer, above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, above-mentioned pressure sensitive adhesive layer is (A2) adhesion strength of 25 ℃ utilizing the above-mentioned pressure sensitive adhesive layer before the radiation exposure of  5.1mm probe assay for more than or equal to 0.5N, and, have at least one characteristic in the following characteristic:
(B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m,
(B2) melt viscosity during 160 ℃ before the radiation exposure is 50～100000Pas.
＜4〉adhesive sheet, it possesses pressure sensitive adhesive layer and substrate layer, bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, above-mentioned pressure sensitive adhesive layer is that the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after (C1) radiation exposure poor (bond strength behind the bond strength-radiation exposure before the radiation exposure) is more than or equal to 100mN/cm, and, have following characteristic at least one characteristic:
(D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, and the tan δ during behind the radiation exposure 180 ℃ is more than or equal to 0.1,
(D2) 120 ℃ of of before the of during radiation exposure is less than or equal to 10MPa of storage modulus (storage modulus storage KURA spring rate), 180 ℃ of of storage modulus of and behind the radiation exposure is less than or equal to 100MPa.
＜5〉adhesive sheet, it possesses pressure sensitive adhesive layer and substrate layer, bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, adhesion strength when above-mentioned pressure sensitive adhesive layer is 25 ℃ of pressure sensitive adhesive layer before and after (C2) radiation exposure poor (bond strengths during behind the bond strength-radiation exposure during before the radiation exposure 25 ℃ 25 ℃) is for more than or equal to 0.1N/  5.1mm probe, and, have following characteristic at least one characteristic:
(D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, the tan δ during behind the radiation exposure 180 ℃ more than or equal to 0.1,
(D2) storage modulus during 120 ℃ before the radiation exposure is less than or equal to 10MPa, and the storage modulus during behind the radiation exposure 180 ℃ is less than or equal to 100MPa.
By forming formation as described above, adhesive sheet of the present invention is to satisfy both to have had enough bounding forces, disperse so that semiconductor element is unlikely when cutting, has low bounding force by after this shining the bounding force that radioactive rays control between above-mentioned pressure sensitive adhesive layer and ground again, so that when taking out, do not damage the adhesive sheet of the such phase cross-demand of each element.Therefore, use adhesive sheet of the present invention to make electronic unit, just can or be able to the action effect that a slice film can be finished each operation of cutting and little chip bonding (die bond).
Description of drawings
Fig. 1 is the sectional drawing of an example of relevant adhesive sheet of the present invention.
Fig. 2 is another routine sectional drawing of relevant adhesive sheet of the present invention.
Fig. 3 is illustrated in the state graph of sticking semiconductor wafer on the relevant adhesive sheet of the present invention.
Fig. 4 is the explanatory view when using about adhesive sheet of the present invention in the cutting process of semiconductor wafer.
Fig. 5 is after being illustrated in process shown in Figure 4, shines the state graph of radioactive rays to adhesive sheet from the inside.
Fig. 6 is after being illustrated in process shown in Figure 5, takes out the figure of the operation of semiconductor element.
Fig. 7 is the semiconductor element of expression taking-up and the figure of pressure sensitive adhesive layer.
Fig. 8 is illustrated in semiconductor element to support state graph with thermo-compressed semiconductor element on the support member.
Fig. 9 is the imidazoles tetraphenyl borate salts (imidazolium tetraphenylborate) that synthesis example 4 obtains 1The H-NMR spectrogram.
Figure 10 is the imidazoles  tetraphenyl borate salts (imidazoliumtetraphenylborate) that synthesis example 5 obtains 1The H-NMR spectrogram.
Figure 11 is the mimic diagram of automatic bond testing machine.
Figure 12 is that the figure of Determination of distance method is overflowed in expression.
Embodiment
＜substrate layer 〉
As the composition that is formed in the substrate layer that uses in the adhesive sheet of the present invention, if see through the composition of radioactive rays, just have no particular limits, can suitably select according to use (for example, whether expansion etc. taking place when taking out).For example can enumerate the ployester series film of pet film etc. particularly, polyolefin films such as polytetrafluoroethylene film, polyethylene film, polypropylene film, poly-methyl pentene film, polyvinyl acetate ester film, the plastics film of polyvinyl chloride film, Kapton etc. etc.
In addition, above-mentioned substrate layer also can be the substrate layer that the different films more than 2 kinds or 2 kinds carries out lamination.In this occasion, combine the film of side with pressure sensitive adhesive layer, consider from the taking-up operation aspect that improves semiconductor element, the modulus in tension under its 25 ℃ is preferably more than or equal to 2000MPa, be more preferably more than or equal to 2200MPa, especially preferably more than or equal to 2400MPa.
In addition, another does not combine the substrate film of side with pressure sensitive adhesive layer, the good aspect of operation, the expansion process big from the unit elongation of film is considered, modulus in tension under its 25 ℃ preferably is less than or equal to 1000MPa, be more preferably and be less than or equal to 800MPa, especially preferably be less than or equal to 600MPa.This modulus in tension is measured according to JIS K7113 number.
Occasion at the substrate layer that uses the substrate film lamination more than 2 kinds or 2 kinds, have no particular limits as its laminating method, can use: the substrate film of making is respectively carried out laminated method, method on certain layer of substrate film is extruded and be laminated to another layer substrate film, on one side the substrate film more than 2 kinds or 2 kinds is extruded and is coated with, the method of fitting in one side, dissolving or dispersion are as the polymkeric substance of the raw material of certain substrate film in solvent, be coated on other substrate film as varnish, the method that adds the heat abstraction solvent, and the known methods such as method that use tackiness agent to fit.
＜pressure sensitive adhesive layer 〉
As the pressure sensitive adhesive layer that in adhesive sheet of the present invention, uses, for example preferably thermoplastic resin, thermopolymerization composition and contain by radiation exposure and produce the pressure sensitive adhesive layer that the compound of base constitutes.By forming such formation, when cutting, have enough bounding forces that semiconductor element does not disperse, after this control bounding force between above-mentioned pressure sensitive adhesive layer and ground by the irradiation radioactive rays, can satisfy when taking out making each element not damage such opposite like this requirement of low bounding force.
(thermopolymerization composition)
In addition; for as above-mentioned thermopolymerization composition; if it is to utilize heat that the polymeric composition takes place; just have no particular limits, for example can enumerate functional groups' such as having glycidyl, acryl, methacryloyl, hydroxyl, carboxyl, isocyanate group, amino, amide group compound.These compounds can use separately, also can make up more than 2 kinds or 2 kinds of uses.If but were considered as the thermotolerance of adhesive sheet, would preferably use to be subjected to thermofixation to bring the heat-curing resin of adhesive effect.As heat-curing resin, for example can enumerate Resins, epoxy, acrylic resin, silicone resin, resol, thermohardening type polyimide resin, urethane resin, melamine resin, urea resin etc., especially from obtain thermotolerance, operation, adhesive sheet aspect that reliability is good is considered, preferably uses Resins, epoxy.When using Resins, epoxy as thermosetting resin, the fits best epoxy curing agent uses.
(Resins, epoxy)
For Resins, epoxy,, just have no particular limits if it is take place to solidify and have adhesive effect.Can use the line style type Resins, epoxy such as difunctional epoxy resin, phenolic aldehyde line style (phenol novolac) Resins, epoxy or cresols line style (cresol novolac) Resins, epoxy of bisphenol type epoxy etc.In addition, can use polyfunctional epoxy resin, glycidyl group amine type Resins, epoxy, contain general known Resins, epoxy such as heterocyclic Resins, epoxy or alicyclic epoxy resin.
As bisphenol A type epoxy resin, can enumerate epoxy resin series (the エ ピ コ-ト シ リ-ズ of japan epoxy resin Co., Ltd. (ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) system, epikoteseries) (Resins, epoxy 807, Resins, epoxy 815, Resins, epoxy 825, Resins, epoxy 827, Resins, epoxy 828, Resins, epoxy 834, Resins, epoxy 1001, Resins, epoxy 1004, Resins, epoxy 1007, Resins, epoxy 1009), the system DER-330 of Dow Chemical (ダ ウ ケ ミ カ Le society), DER-301, DER-361, and the system YD8125 of Toto Kasei KK, YDF8170 etc.As the phenolic aldehyde linear epoxy resin, can enumerate Resins, epoxy 152, the Resins, epoxy 154 of japan epoxy resin Co., Ltd. system, the EPPN-201 of Nippon Kayaku K. K's system, the DEN-438 of Dow Chemical's system etc.In addition, as the ortho-cresol linear epoxy resin, can enumerate EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, the EOCN-1027 of Nippon Kayaku K. K's system, or Toto Kasei KK makes YDCN701, YDCN702, YDCN703, YDCN704 etc.As polyfunctional epoxy resin, can enumerate the Epon 1031S of japan epoxy resin Co., Ltd. system, Resins, epoxy (the ア ラ Le ダ イ ト of チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ Co., Ltd. system, araldite) 0163, Resins, epoxy (デ Na コ-Le, Denacol) EX-611, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-421, EX-411, the EX-321 etc. of society of Na ガ セ ケ system テ Star Network ス Co., Ltd. system.As amine type Resins, epoxy, can enumerate Resins, epoxy 604, the YH-434 of Toto Kasei KK's system, the TETRAD-X and the TETRAD-C of aerochemistry Co., Ltd. of Mitsubishi system of japan epoxy resin Co., Ltd. system, the ELM-120 of Sumitomo Chemical Co's system etc.As containing heterocyclic Resins, epoxy, can enumerate Resins, epoxy (ア ラ Le ダ イ ト, araldite) PT810, the ERL4234 of UCC corporate system, ERL4299, ERL4221, the ERL4206 etc. of チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ Co., Ltd. system.These Resins, epoxy can use separately or also can make up more than 2 kinds or 2 kinds of uses.
(epoxy curing agent)
When using Resins, epoxy, preferably use epoxy curing agent.As epoxy curing agent, can use normally used known solidifying agent, for example can enumerate amine, polymeric amide, acid anhydrides, polysulphide, boron trifluoride, as dihydroxyphenyl propane, Bisphenol F, bisphenol S in a molecule, have more than 2 or 2 the bisphenols of phenolic hydroxyl group, resol such as phenolic aldehyde line style resin, dihydroxyphenyl propane line style resin or cresols line style resin etc.On special good this aspect of electrocorrosion-resisting when moisture absorption, preferentially select the resol of phenolic aldehyde line style resin, dihydroxyphenyl propane line style resin or cresols line style resin etc.
The best solidifying agent of conduct in above-mentioned phenolic resin curative, for example can enumerate Dainippon Ink. ﹠ Chemicals Inc's system, trade(brand)name: phenolite resol (Off エ ノ ラ イ ト) LF2882, phenolite resol LF2822, phenolite resol TD-2090, phenolite resol TD-2149, phenolite resol VH-4150, phenolite resol VH4170, bright and change into Co., Ltd.'s system, trade(brand)name: H-1, japan epoxy resin Co., Ltd. system, trade(brand)name: エ ピ キ ユ ア MP402FPY, エ ピ キ ユ ア YL6065, エ ピ キ ユ ア YLH129B65 and Mitsui Chemicals, Inc's system, trade(brand)name: ミ レ Star Network ス XL, ミ レ Star Network ス XLC, ミ レ Star Network ス RN, ミ レ Star Network ス RS, ミ レ Star Network ス VR etc.
(producing the compound of base by radiation exposure)
The compound that produces base by radiation exposure is the compound that produces base when radiation exposure, and the base that is produced rises the curing reaction speed of thermosetting resin.As the base that produces, consider from reactive, curing speed aspect, preferentially select the strong-base group compound.In general, as the index of base, use be the logarithmic pKa value of acid dissociation constant, preferentially be chosen in pKa value in the aqueous solution and be base, preferably more than or equal to 9 base more than or equal to 7.In addition, produce the compound of base by radiation exposure, the preferential compound that produces base by the rayed of wavelength 150～750nm that uses, in order when using general light source, to produce base, preferably select the compound that can produce base by the rayed of 250～500nm for use with good efficiency.
As the example that shows such base, can enumerate imidazoles, 2, the 4-methylimidazole, imdazole derivatives such as 1-Methylimidazole, piperazine, 2, bridged piperazine derivatives such as 5-lupetazin, piperidines, 1, piperidine derivatives such as 2-lupetidine, proline derivative, Trimethylamine 99, triethylamine, trialkylamine derivatives such as trolamine, at 4-methylamino pyridine, 4 pyridine derivates that amino or alkylamino replacement take place of 4-dimethylamino pyridine etc., tetramethyleneimine, pyrrolidin derivatives such as positive crassitude, triethylenediamine, 1,8-diazabicyclo (5,4,0) undecene-1 ester ring type sulfonamide derivativess such as (DBU), the benzyl methylamine, benzyldimethylamine, the benzyl amine derivative of benzyl diethylamine etc. etc.
As the above-mentioned material that produces base by radiation exposure, for example can use 12 volumes at Journal ofPhotopolymer Science and Technology, 313～314 (1999) or Chemistryof Materials 11 volume, the quaternary ammonium salt derivative that 170～176 (1999) are put down in writing in waiting.These quaternary ammonium salt derivatives, owing to produce the trialkylamine of high base by the irradiation of active ray, so be suitable for the curing of Resins, epoxy most.
In addition, also can use carbamic acid derivative of in Journal of American Chemical Society 118 volume 12925 pages (1996) or Polymer Journal 28 volumes 795 pages (1996) wait, putting down in writing or the 9 oxime derivate that produces primary amino by the irradiation of active ray.
In addition, as the compound that produces base by above-mentioned radiation exposure, the alpha-amino group ketone compound is the compound that can be fit to use in the present invention.Specifically, as the optical free radical initiator, can use commercially available 2-methyl isophthalic acid (4-(methylthio group) phenyl)-2-morpholino propane-1-ketone (Ciba Speciality Chemicals corporate system イ Le ガ キ ユ ア 907), 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1-ketone (Ciba Speciality Chemicals corporate system イ Le ガ キ ユ ア 369), hexa-aryl bi-imidazole derivative (substituting groups such as halogen, alkoxyl group, nitro, cyano group can be replaced by phenyl), benzisoxa  ketone derivatives etc.
Above-mentioned alpha-amino group ketone compound, before the irradiation radioactive rays, because steric barrier, so do not have the curing promoter action of thermosetting resin, but by the irradiation radioactive rays, the alpha-amino group ketone compound just dissociates, and above-mentioned steric barrier reduces, and therefore infers that it has the curing promoter action of thermosetting resin.
Except the base initiator that causes by above-mentioned active ray, produce the base compound and also can carry out the curing of Resins, epoxy by light Fu Lisi (Off リ one ス) rearrangement, light claisen (Cleisen) rearrangement or Ku Ertisi (Curtius) rearrangement, Si Difen (Stevens) rearrangement.
(amine imide compound)
As producing the compound of base through radiation exposure, except above-claimed cpd, also can use the amine imide compound by what use among the present invention.The amine imide compound if produce the compound of base by the irradiation of active light, just has no particular limits.
For example can enumerate particularly with following general formula (XXV) or (XXVI) expression compound.
Figure A20061010028700151
(in the formula, R 1, R 2, R 3Can enumerate benzyl that phenyl, benzyl, electron-donating group and/or electron withdrawing group that phenoxyalkyl, phenyl, electron-donating group and/or the electron withdrawing group of cycloalkenyl, the carbonatoms 1～6 of cycloalkyl, the carbonatoms 4～8 of alkoxyl group, the carbonatoms 4～8 of alkyl, the carbonatoms 1～8 of hydrogen, carbonatoms 1～8 replace replace etc. independently.As the alkyl of carbonatoms 1～8, the alkyl on straight chain, also comprise sec.-propyl, isobutyl-, the tertiary butyl etc.In these substituting groups, consider the alkyl of preferred carbonatoms 1～8, the cycloalkyl of carbonatoms 6～8, the phenoxyalkyl of carbonatoms 1～6 from aspects such as synthetic simplicity, the imido solvabilities of amine.In addition, R 4Alkyl, hydroxyl, the cycloalkyl of carbonatoms 4～8, the alkoxyl group of carbonatoms 1～5, the phenyl of representing carbonatoms 1～5 independently.)
Ar in the above-mentioned general formula (XXV) 1Be aromatic series base with general formula (IV)～(XVI) expression, in addition, the Ar in the above-mentioned general formula (XXVI) 2Preferably with the aromatic series base of following formula (XVII)～(XXV) expression.From and Ar 1Identical thermostability, absorbing wavelength aspect are considered, as R 29～R 36Substituting group, preferential carbonyl, cyano group, the nitro of selecting to belong to the carbonatoms 1～6 of electron withdrawing group.
Synthesizing of above-mentioned amine imide compound, can use known method.For example, as Encyclopediaof Polymer Science and Engineering, John Wiley ﹠amp; Sons Ltd. (1985), the 1st volume, record in 740 pages can obtain from the carboxylicesters of correspondence and the reaction of halogenation hydrazides and sodium alkoxide or the reaction of carboxylicesters and hydrazides and epoxy compounds.If consider synthetic simplicity, security, then preferential especially the selection carried out the synthetic method from the carboxylicesters of correspondence and hydrazides and epoxy compounds.About synthesis temperature, generated time, just unrestricted as long as it can not decompose by employed starting material, but generally under 0～100 ℃ temperature, pass through to stir 30 minutes～7 days, just can access the targeted amine imide compound.
(imidazolium salts)
In addition, the compound that radiation exposure produces base that passes through as using among the present invention except above-claimed cpd, can also use imidazolium salts.As imidazolium salts, for example can enumerate with the imidazolium salts compound shown in general formula (1) or (2).
Figure A20061010028700161
(in the formula, R 1, R 2, R 3, R 4Represent hydrogen independently, the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8, the cycloalkyl of carbonatoms 4～8, the cycloalkenyl of carbonatoms 4～8, the phenoxyalkyl of carbonatoms 1～6, the benzene alkyl of carbonatoms 1～6, the Qing Wanji of carbonatoms 1～6, the hydroxyalkyl of carbonatoms 1～6, phenyl, the phenyl that electron-donating group and/or electron withdrawing group replace, benzyl, the benzyl that electron-donating group and/or electron withdrawing group replace, nitro, cyano group, sulfydryl, thiomethyl, fluorine, bromine, chlorine, iodine.)
In addition, Ar 1It is aromatic series base with following formula (I)～(XIV) expression.
Figure A20061010028700171
(in the formula, R 5～R 28Be hydrogen independently, the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8, the alkylthio of carbonatoms 1～8, the cycloalkyl of carbonatoms 4～8, the cycloalkenyl of carbonatoms 4～8, amino, the alkylamino of carbonatoms 1～6, the dialkylamino of carbonatoms 1～3, the morpholino base, sulfydryl, hydroxyl, the hydroxyalkyl of carbonatoms 1～6, fluorine, chlorine, halogens such as bromine, the ester group of carbonatoms 1～6, the carbonyl of carbonatoms 1～6, aldehyde radical, cyano group, trifluoromethyl, nitro, phenyl, the phenyl that electron-donating group and/or electron withdrawing group replace, the benzyl that electron-donating group and/or electron withdrawing group replace.And T, U, V, W, Y, Z represent any in carbon, nitrogen, oxygen, the sulphur atom independently in the formula.)
In addition, Ar 2It is aromatic series base with following formula (XV)～(XXIII) expression.
Figure A20061010028700181
(in the formula, R 29～R 36Be hydrogen independently, the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8, the alkylthio of carbonatoms 1～8, the cycloalkyl of carbonatoms 4～8, the cycloalkenyl of carbonatoms 4～8, amino, the alkylamino of carbonatoms 1～6, the dialkylamino of carbonatoms 1～3, the morpholino base, sulfydryl, hydroxyl, the hydroxyalkyl of carbonatoms 1～6, fluorine, chlorine, halogens such as bromine, the ester group of carbonatoms 1～6, the carbonyl of carbonatoms 1～6, aldehyde radical, cyano group, trifluoromethyl, nitro, phenyl, the phenyl that electron-donating group and/or electron withdrawing group replace, the benzyl that electron-donating group and/or electron withdrawing group replace.And A, B, D, E are any in carbon, nitrogen, oxygen, the sulphur atom independently in the formula, they also can with alkyl, oxygen, the sulphur combination of carbon, nitrogen, carbonatoms 1～6.)
In addition, X -Be dialkyl group two thiocarbamides of carbonatoms 1～6, with the boric acid of following formula (XXIV) expression.
Figure A20061010028700191
(in the formula, R 37～R 40Be the alkyl, phenyl of hydrogen, fluorine, carbonatoms 1～6, fluorophenyl, the imidazolyl that at least more than one fluorine replaces independently.)
Synthetic with the imidazole salts compound of the above-mentioned general formula (1) that produces base by rayed or (2) expression of using among the present invention, can use known method, if but consider synthetic simplicity, security, then preferential the selection as shown in the formula shown in (XXVII), behind alkyl halide ketone derivatives and the synthetic imidazolium salts halogen of imdazole derivatives, by anion exchange reaction, the method for synthetic imidazolium salts.
About synthesis temperature, generated time, if employed starting material do not decompose, just be not particularly limited, but general under 0～100 ℃ temperature, by 30 minutes～7 days stirring, just can access target imidazolium salts compound.Since these compounds in room temperature, do not shine the reactivity that can not demonstrate under the state of radioactive rays with Resins, epoxy, therefore have the very good feature of storage stability at room temperature.
The usage quantity of the compound that produces base by radiation exposure shown in so far routine, the Resins, epoxy of relative 100 parts by weight, preferably 0.01～200 parts by weight preferably are more preferably 0.02～150 parts by weight.If the tendency that usage quantity less than 0.01 parts by weight, can exist the bounding force when taking out to be difficult to reduce, according to employed compound difference, thermotolerance also reduces.In addition, if usage quantity surpasses 200 parts by weight, the tendency that can exist the rerum natura as the characteristic storage stability film of adhesive films to worsen.
(singlet state sensitizing agent, triplet state sensitizing agent)
In addition, for the height absorptionization that reaches irradiates light, the purpose of high sensitivityization, also can in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention, add sensitizing agent.As employed sensitizing agent, only otherwise solidification compound is brought baneful influence, just can use known singlet state sensitizing agent, triplet state sensitizing agent.
As above-mentioned sensitizing agent, the aromatics derivative of for example suitable use naphthalene, anthracene, pyrene etc., carbazole derivative, benzophenone derivates, st-yrax derivative, thioxanthone derivates, coumarin derivatives etc.
The usage quantity of above-mentioned sensitizing agent, need be with reference to the absorbing wavelength and the molar absorptivity of sensitizing agent, but the base that produces by radiation exposure with respect to (c) of 1 parts by weight, be preferably 0.01～10 parts by weight, more preferably 0.1～5 parts by weight are preferably 0.1～2 parts by weight especially.If sensitizing agent is equal to or less than 0.01 parts by weight, then the efficient of photoabsorption just reduces, if surpass 10 parts by weight, then has the tendency of light transmission rate variation.
The sensitizing agent that uses among the present invention as long as solidification compound is not brought baneful influence, just can use known singlet state sensitizing agent, triplet state sensitizing agent.For example be fit to use aromatics derivative, carbazole derivative, aromatic carbonyl, benzophenone derivates, st-yrax derivative, thioxanthone derivates, coumarin derivativess etc. such as naphthalene, anthracene, pyrene.Among these, as the singlet state sensitizing agent, preferred especially naphthalene derivatives, anthracene derivant, carbazole derivative, as the triplet state sensitizing agent, preferred especially thioxanthone derivates, benzophenone derivates, st-yrax derivative.For example, can enumerate 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodine naphthalene, 2-iodine naphthalene, 1-naphthols, beta naphthal, with the compound of following general formula (I)～(XXIII) expression,
Figure A20061010028700211
(in the formula, R 5～R 28Be hydrogen independently; the alkyl of carbonatoms 1～8; the alkoxyl group of carbonatoms 1～8; the alkylthio of carbonatoms 1～8; the cycloalkyl of carbonatoms 4～8; the cycloalkenyl of carbonatoms 4～8; amino; the alkylamino of carbonatoms 1～6; the dialkylamino of carbonatoms 1～3; the morpholino base; sulfydryl; hydroxyl; the hydroxyalkyl of carbonatoms 1～6; fluorine; chlorine; halogens such as bromine; the ester group of carbonatoms 1～6; the carbonyl of carbonatoms 1～6; aldehyde radical; cyano group; trifluoromethyl; nitro; benzoyl; phenyl; the phenyl that electron-donating group and/or electron withdrawing group replace; the benzyl that electron-donating group and/or electron withdrawing group replace.And T, U, V, W, Y, Z represent any in carbon, nitrogen, oxygen, the sulphur atom independently in the formula.)
(in the formula, R 29～R 36Be hydrogen independently, the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8, the alkylthio of carbonatoms 1～8, the cycloalkyl of carbonatoms 4～8, the cycloalkenyl of carbonatoms 4～8, amino, the alkylamino of carbonatoms 1～6, the dialkylamino of carbonatoms 1～3, the morpholino base, sulfydryl, hydroxyl, the hydroxyalkyl of carbonatoms 1～6, fluorine, chlorine, halogens such as bromine, the ester group of carbonatoms 1～6, the carbonyl of carbonatoms 1～6, aldehyde radical, cyano group, trifluoromethyl, nitro, phenyl, the phenyl that electron-donating group and/or electron withdrawing group replace, the benzyl that electron-donating group and/or electron withdrawing group replace.And A, B, D, E are any in carbon, nitrogen, the oxygen sulphur atom independently in the formula, they can with alkyl, oxygen, the sulphur combination of carbon, nitrogen, carbonatoms 1～6.)。In addition; can enumerate the 1-methoxynaphthalene; the 2-methoxynaphthalene; 1; the 4-dicyano naphthalene; anthracene; 1; 2-benzene embedding anthracene; 9; 10-two chrloroanthracenes; 9; the 10-dibromoanthracene; 9; the 10-diphenylanthrancene; 9-cyano group anthracene; 9; 10-dicyano anthracene; 2; 6; 9; 10-four cyano anthracene; carbazole; 9-methyl carbazole; the 9-phenyl carbazole; 9-propylene (プ ロ ペ)-2-base (イ ニ Le)-9H-carbazole; 9-propyl group-9H-carbazole; the 9-vinylcarbazole; 9H-carbazole-9-ethanol; 9-methyl-3-nitro-9H-carbazole; 9-methyl-3; 6-dinitrobenzene-9H-carbazole; 9-capryloyl carbazole; 9-carbazole methyl alcohol; 9-carbazole propionic acid; 9-carbazole propionitrile; 9-decyl-3; 6-dinitrobenzene-9H-carbazole; 9-ethyl-3; 6-dinitrobenzene-9H-carbazole; 9-ethyl-3-nitro carbazole; the 9-ethyl carbazole; 9-sec.-propyl carbazole; 9-(ethoxycarbonylmethyl group) carbazole; 9-(morpholino methyl) carbazole; the 9-acetyl carbazole; 9-allyl group carbazole; 9-benzyl-9H-carbazole; 9-Carbazoleacetic Acid; 9-(2-nitrophenyl) carbazole; 9-(4-p-methoxy-phenyl) carbazole; 9-(1-oxyethyl group-2-methyl-propyl group)-9H-carbazole; 3-nitro carbazole; the 4-hydroxycarbazole; 3; 6-dinitrobenzene-9H-carbazole; 3; 6-phenylbenzene-9H-carbazole; the 2-hydroxycarbazole; 3; 6-diacetyl-9-ethyl carbazole; benzophenone; the 4-phenyl benzophenone; 4; 4 '-two (dimethoxy) benzophenone; 4; 4 '-two (dimethylamino) benzophenone; 4; 4 '-two (diethylin) benzophenone; 2-benzoyl M-nitro benzoic acid methyl esters; 2 methyl benzophenone; 3-methyldiphenyl ketone; 4-methyldiphenyl ketone; 3; 3 '-dimethyl-4-methoxy benzophenone; 2; 4; the 6-tri-methyl benzophenone; [4-(4-methylbenzene sulfenyl) phenyl]-phenyl ketone; xanthone; thioxanthone; the 2-clopenthixal ketone; the 4-clopenthixal ketone; the 2-isopropyl thioxanthone; the 4-isopropyl thioxanthone; 2; 4-dimethyl thioxanthone; 2; the 4-diethyl thioxanthone; 1-chloro-4-propoxy-thioxanthone; st-yrax; benzoin methyl ether; Benzoin ethyl ether; benzoin isopropyl ether; the st-yrax positive propyl ether; the st-yrax n-butyl ether; benzoin isobutyl ether; 2; 2-dimethoxy base-1; 2-phenylbenzene ethyl ketone; 2; 2-diethoxy-1,2-phenylbenzene ethyl ketone etc.These also can make up multiple use except independent use.
As described in so far, (c) produce the compound of base by rayed, because in room temperature, do not shine the reactivity that does not demonstrate under the state of radioactive rays with thermopolymerization compound such as Resins, epoxy, therefore have the very good feature of storage stability at room temperature.
(thermoplastic resin)
To improve film formation property is purpose, can contain thermoplastic resin in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention.
Above-mentioned thermoplastic resin, if have thermoplastic resin, perhaps have thermoplasticity in its uncured state at least, after heating, form the resin of crosslinking structure, just have no particular limits, but better be Tg (glass transformation temperature) for-50～100 ℃, weight-average molecular weight are 100000～1000000 thermoplastic resin, perhaps preferably Tg is that 10～100 ℃, weight-average molecular weight are 5000～200000 thermoplastic resin.
As the former thermoplastic resin, preferably use the polymkeric substance that contains the functional monomer, thermoplastic resin as the latter, for example can enumerate polyimide resin, polyamide resin, polyetherimide resin, polyamide-imide resin, vibrin, polyesterimide resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide, polyether ketone resin etc., wherein, be best especially with the polyimide resin.
As the functional group in containing above-mentioned functional monomer's polymkeric substance, for example can enumerate glycidyl, acryl, methacryloyl, hydroxyl, carboxyl, isocyanuric acid ester group, amino, amide group etc., be best especially with the glycidyl.In particular, with (methyl) acrylic copolymer that contains glycidyl of the functional monomer of containing glycidyl acrylate or glycidyl methacrylate etc. etc. for good, and with thermosetting resin such as Resins, epoxy be non-mix for better.
(weight-average molecular weight that contains the functional monomer more than or equal to 100,000 high molecular weight components)
As the above-mentioned weight-average molecular weight that contains the functional monomer more than or equal to 100,000 high molecular weight components, for example can enumerate the functional monomer of containing glycidyl acrylate or glycidyl methacrylate etc. and contain weight-average molecular weight more than or equal to (methyl) acrylic copolymer of 100,000 glycidyl etc., wherein, particularly preferably be with Resins, epoxy be the non-material that mixes.
As above-mentioned (methyl) acrylic copolymer that contains glycidyl, for example can use (methyl) acrylate copolymer, acrylic rubber etc., with acrylic rubber for better.Acrylic rubber is to be main component with the acrylate, mainly is the rubber that the multipolymer by the multipolymer of butyl acrylate and vinyl cyanide etc. or ethyl propenoate and vinyl cyanide etc. constitutes.
Above-mentioned so-called functional monomer is meant the monomer with functional group, as such monomer, preferably uses glycidyl acrylate or glycidyl methacrylate etc.More than or equal to (methyl) acrylic copolymer that contains glycidyl of 100,000, for example can enumerate the HTR-860P-3 of Na ガ セ ケ system テ Star Network ス Co., Ltd. system etc. as such weight-average molecular weight.
The amount of the repeating unit of the above-mentioned Resins, epoxy that contains glycidyl acrylate or glycidyl methacrylate etc. is preferably 0.5～6.0 weight %, and more preferably 0.5～5.0 weight % is preferably 0.8～5.0 weight % especially.If the amount of repeating unit that contains glycidyl just can be guaranteed bounding force in this scope, meanwhile can prevent gelation.
Above-mentioned functional monomer as beyond glycidyl acrylate, the glycidyl methacrylate for example can enumerate (methyl) ethyl propenoate, (methyl) butyl acrylate etc., and they can use separately or make up more than 2 kinds or 2 kinds and use.Moreover in the present invention, so-called (methyl) ethyl propenoate is represented ethyl propenoate and two kinds of situations of Jia Jibingxisuanyizhi.Mixture ratio when being used in combination the functional monomer, the Tg that should consider to contain (methyl) acrylic copolymer of glycidyl decides, and Tg is preferably and is greater than or equal to-10 ℃.When Tg was greater than or equal to-10 ℃, the tackiness of the pressure sensitive adhesive layer under the B step state was suitable, thereby does not have problems on operability.
Make above-mentioned monomer polymerization, when making the weight-average molecular weight contain the functional monomer,, having no particular limits, for example can use methods such as pearl polymerization, solution polymerization for polymerization process more than or equal to 100,000 high molecular weight components.
In the present invention, be more than or equal to 100,000 though contain the weight-average molecular weight of functional monomer's high molecular weight components, be preferably 300,000～3,000,000, more preferably 500,000～2,000,000.If intensity, pliability and tackiness when weight-average molecular weight in this scope, is then laminated shape or film like are suitable, in addition,, therefore can guarantee the circuit fillibility that connects up because it is suitably mobile.Moreover in the present invention, so-called weight-average molecular weight is to measure by illustrated gel permeation chromatography in the evaluation method hurdle below, and the value of using the polystyrene standard measuring line to converse.
In addition, the weight-average molecular weight that contains the functional monomer is more than or equal to the usage quantity of 100,000 high molecular weight components, and the thermopolymerization composition of relative 100 parts by weight is preferably 10～400 parts by weight.If in this scope, then can guarantee storage modulus and the control of the flowability when being shaped, and also can fully obtain the operability under the high temperature.The usage quantity of high molecular weight components is 15～350 parts by weight more preferably, are preferably 20～300 parts by weight especially.
(polyimide resin)
In above-mentioned thermoplastic resin,, can obtain by making tetracarboxylic dianhydride and diamines carry out condensation reaction with known method as the polyimide resin of one of the best.That is, in organic solvent, be lower than or, be preferably under 0～60 ℃, mole or roughly equimolar tetracarboxylic dianhydride and diamines (the interpolation order of each composition arbitrarily) are reacted less than 80 ℃ in temperature of reaction.Along with the carrying out of reaction, the viscosity of reaction solution little by little rises, and generates the polyamic acid as the precursor of polyimide.
Above-mentioned polyamic acid by adding thermal depolymerization under 50～80 ℃ temperature, and can be adjusted its molecular weight.
Can make above-mentioned reactant (polyamic acid) dehydration closed-loop and obtain polyimide resin.Dehydration closed-loop can be undertaken by the hot closed loop method of using heat treated and the chemical closed loop method of using dewatering agent.
For as the raw material of polyimide resin and the tetracarboxylic dianhydride who uses have no particular limits, for example, can use 1,2-(ethylidene) two (trimellitic acid 1,2-anhydrides) (ト リ メ リ テ Yi ト No water thing), 1,3-(trimethylene) two (trimellitic acid 1,2-anhydrides), 1,4-(tetramethylene) two (trimellitic acid 1,2-anhydrides), 1,5-(pentamethylene) two (trimellitic acid 1,2-anhydrides), 1,6-(hexa-methylene) two (trimellitic acid 1,2-anhydrides), 1,7-(heptamethylene) two (trimellitic acid 1,2-anhydrides), 1,8-(eight methylene radical) two (trimellitic acid 1,2-anhydrides), 1,9-(nine methylene radical) two (trimellitic acid 1,2-anhydrides), 1,10-(decamethylene) two (trimellitic acid 1,2-anhydrides), 1,12-(ten dimethylenes) two (trimellitic acid 1,2-anhydrides), 1,16-(ten hexa-methylenes) two (trimellitic acid 1,2-anhydrides), 1,18-(18 methylene radical) two (trimellitic acid 1,2-anhydrides), pyromellitic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 2,2-two (3,4-dicarboxyl phenyl) propane dianhydride, 2, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 2-, 1, two (2,3-dicarboxyl phenyl) the propane dianhydrides of 1-, 1,1-two (3,4-dicarboxyl phenyl) ethane dianhydride, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (2,3-two carboxyphenyls) methane two anhydrides, two (3,4-two carboxyphenyls) methane two anhydrides, two (3,4-two carboxyphenyls) sulfone two anhydrides, 3,4,9, the 10-perylenetetracarboxylic dianhydride, two (3,4-two carboxyphenyls) ether two anhydrides, benzene-1,2,3, the 4-tetracarboxylic dianhydride, 3,4,3 ', 4 '-benzo benzophenone tetracarboxylic dianhydride, 2,3,2 ', 3 '-benzo benzophenone tetracarboxylic dianhydride, 3,3,3 ', 4 '-benzo benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,4,5-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1,4,5, the 8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-1,4,5, the 8-tetracarboxylic dianhydride, luxuriant and rich with fragrance-1,8,9, the 10-tetracarboxylic dianhydride, pyrazine-2,3,5, the 6-tetracarboxylic dianhydride, thiophene-2,3,5, the 6-tetracarboxylic dianhydride, 2,3,3 ', 4 '-biphenyl carboxylic acids dianhydride, 3,4,3 ', 4 '-biphenyl carboxylic acids dianhydride, 2,3,2 ', 3 '-biphenyl carboxylic acids dianhydride, two (3,4-two carboxyphenyls) dimethylsilane two anhydrides, two (3,4-two carboxyphenyls) tolyl silane two anhydrides, two (3,4-two carboxyphenyls) diphenyl silane two anhydrides, 1, two (3,4-two carboxyphenyl dimetylsilyl) benzene two anhydrides of 4-, 1,3-two (3,4-two carboxyphenyls)-1,1,3,3-tetramethyl-bicyclohexane two anhydrides, TOPOT 2,2 (anhydrous trimellitate), the ethylidene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, naphthane-1,4,5, the 8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro-naphthalene-1,2,5, the 6-tetracarboxylic dianhydride, pentamethylene-1,2,3, the 4-tetracarboxylic dianhydride, tetramethyleneimine-2,3,4, the 5-tetracarboxylic dianhydride, 1,2,3,4-tetramethylene tetracarboxylic dianhydride, two (outer two rings) [2,2,1] heptane-2, the 3-dicarboxylic acid dianhydride, two rings [2,2,2]-Xin-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride, 2,2-two (3,4-dicarboxyl phenyl) hexafluoropropane dianhydride, 2, two [4-(3, the 4-dicarboxyl phenyl) phenyl] hexafluoropropane dianhydrides of 2-, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenyl sulfide dianhydride, 1, two (2-hydroxyl hexafluoro sec.-propyl) benzene of 4-two (trimellitic acid 1,2-anhydride), 1, two (2-hydroxyl hexafluoro sec.-propyl) benzene of 3-two (trimellitic acid 1,2-anhydride), 5-(2,5-titanium dioxide tetrahydrofuran base)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid dianhydride, tetrahydrofuran (THF)-2,3,4,5-tetracarboxylic dianhydrides etc. also can use in them a kind or and with more than 2 kinds or 2 kinds.
In addition, the diamines that uses as the raw material of polyimide, have no particular limits, for example can use O-Phenylene Diamine, mphenylenediamine, Ursol D, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenylmethane, 3,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide methane, two (4-amino-3, the 5-xylyl) methane, two (4-amino-3, the 5-diisopropylbenzyl) methane, 3,3 '-diamino-diphenyl methylene fluoride, 3,4 '-diamino-diphenyl methylene fluoride, 4,4 '-diamino-diphenyl methylene fluoride, 3,3 '-diaminodiphenylsulfone(DDS), 3,4 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diamino diphenyl sulfide, 3,4 '-diamino diphenyl sulfide, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino benzophenone, 3,4 '-diamino benzophenone, 4,4 '-diamino benzophenone, 2, two (3-aminophenyl) propane of 2-, 2,2 '-(3,4 '-diamino phenylbenzene) propane, 2, two (4-aminophenyl) propane of 2-, 2, two (3-aminophenyl) HFC-236fa of 2-, 2,2-(3,4 '-diamino-diphenyl) HFC-236fa, 2, two (4-aminophenyl) HFC-236fa of 2-, 1, two (the 3-ammonia phenoxy group) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 3,3 '-(1, two (the 1-methyl ethylidene) dianilines of 4-phenylene, 3,4 '-(1, two (the 1-methyl ethylidene) dianilines of 4-phenylene, 4,4 '-(1, two (the 1-methyl ethylidene) dianilines of 4-phenylene, 2, two (4-(3-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, 2, two (4-(3-amino-benzene oxygen) phenyl) HFC-236fa of 2-, 2, two (4-(4-amino-benzene oxygen) phenyl) HFC-236fa of 2-, two (4-(3-amino-benzene oxygen) phenyl) sulfide, two (4-(4-amino-benzene oxygen) phenyl) sulfide, two (4-(3-amino-benzene oxygen) phenyl) sulfone, two (4-(4-amino-benzene oxygen) phenyl) sulfone, 3, aromatic diamines such as 5-diamino M-nitro benzoic acid, 1, the 2-diaminoethanes, 1, the 3-diaminopropanes, 1, the 4-diaminobutane, 1,5-diamino pentane, 1, the 6-diamino hexane, 1,7-diamino heptane, 1,8-diamino octane, 1,9-diamino nonane, 1, the 10-diamino decane, 1,11-diamino undecane, 1,12-diamino dodecane, 1, the 2-diamino-cyclohexane, with following general formula (3)
(in the formula, R 1And R 2The bivalent hydrocarbon radical of expression carbonatoms 1～30 separately can be identical, also can be different, and R 3And R 4Expression univalent alkyl, separately can be identical, also can be different, m is the integer more than or equal to 1) expression diamino polysiloxane, 1, aliphatic diamines such as polyoxyalkylenes diamines such as two (aminomethyl) hexanaphthenes of 3-, the system ジ エ of サ Application テ ケ ノ ケ ミ カ Le Co., Ltd. Off ア ミ Application D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2001, EDR-148 etc. also can use in them a kind or and with more than 2 kinds or 2 kinds.The Tg of above-mentioned carboxylic acid polyimide resin is preferably 0～200 ℃, and weight-average molecular weight is preferably 10,000～200,000.
(other composition)
Because of having above-described composition,,,, can use as other compositions shown below perhaps according to the structure of applied semiconductor packages etc. for further making the characteristic optimizing so can access the adhesive sheet of characteristic good.
(radioactive rays polymerizability composition)
In order to improve polymerization susceptibility, can contain radioactive rays polymerizability composition, as the composition that is formed in the pressure sensitive adhesive layer that uses in the adhesive sheet of the present invention to radiation exposure.As radioactive rays polymerizability composition, have no particular limits, for example, can use methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, butyl acrylate, butyl methacrylate, 2-EHA, methacrylic acid 2-ethylhexyl, vinylformic acid amylene ester, the vinylformic acid tetrahydro furfuryl ester, the methacrylic acid tetrahydro furfuryl ester, diacrylate glycol ether ester, the diacrylate triethyleneglycol ester, diacrylate Tetraglycol 99 ester, dimethacrylate glycol ether ester, the dimethacrylate triethyleneglycol ester, dimethacrylate Tetraglycol 99 ester, trimethylolpropane diacrylate, Viscoat 295, the TriMethylolPropane(TMP) dimethacrylate, trimethylolpropane trimethacrylate, 1, the 4-butylene glycol diacrylate, 1, the 6-hexanediyl ester, 1, the 4-butylene glycol dimethacrylate, 1, the 6-hexanediol dimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythritol acrylate trimethyl, tetramethylolmethane tetramethyl-acrylate, dipentaerythritol acrylate, Dipentaerythritol hexamethyl acrylate, vinylbenzene, Vinylstyrene, the 4-Vinyl toluene, 4-vinylpridine, the N-vinyl pyrrolidone, vinylformic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxyl ethyl ester, 1,3-acryloxy-2-hydroxy propane, 1,2-iso-butylene acyl-oxygen base-2-hydroxy propane, methylene-bisacrylamide, N,N-DMAA, N hydroxymethyl acrylamide, the triacrylate of tris, with following general formula (4)
Figure A20061010028700291
(in the formula, R 1And R 2Expression hydrogen or methyl, q and r are the integers more than or equal to 1)
The compound, glycols of expression and with general formula (5)
Figure A20061010028700292
(in the formula, n is 0～1 integer, R 3Be the divalent of carbonatoms 1～30 or the organic group of 3 valencys)
The isocyanate compound of expression, and by with general formula (6)
Figure A20061010028700293
(in the formula, R 4Be hydrogen or methyl, R 5Be ethylidene or propylidene)
Urethanum acrylate that the compound of expression constitutes or urethanum methacrylic ester, with general formula (7)
H 2N-R 6-NH 2 (7)
(in the formula, R 6The divalent organic group of expression carbonatoms 2～30)
The diamines of expression, and with general formula (8)
Figure A20061010028700301
(in the formula, n is 0～1 integer, R 7Be the divalent of carbonatoms 1～30 or the organic group of 3 valencys)
The isocyanate compound of expression, and by with general formula (9)
Figure A20061010028700302
(in the formula, n is 0～1 integer)
The urea methacrylic ester that the compound of expression constitutes, the compound that has 1 functional group of at least one ethene unsaturated group and oxyethane ring, isocyanate group, hydroxyl, carboxyl etc. in containing functional group's ethylene copolymer carry out addition reaction and have the radioactive rays polymerizability copolymerization etc. of ethene unsaturated group on the side chain that obtains.These radioactive rays polymerizable compounds can use separately or make up more than 2 kinds or 2 kinds and use.
In addition, use the compound as produce the solidified base that promotes above-mentioned Resins, epoxy by radiation exposure, also can have the radioactive rays polymerizability.
(curing catalyst)
In addition, in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention, can also add curing catalyst.For curing catalyst, have no particular limits, can use imidazoles, cyanoguanidine derivative, dicarboxyl acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenyl borate salts, 2-ethyl-4-methylimidazole tetraphenyl borate salts, 1,8-nitrine two rings (5,4,0) undecylene-7-tetraphenyl borate salts etc.They can use separately, perhaps can make up more than 2 o'clock or 2 kinds and use.
The addition of curing catalyst, the thermopolymerization composition of relative 100 parts by weight is preferably 0.1～5 parts by weight, more preferably 0.2～3 parts by weight.If addition in this scope, then can have solidified nature and storage stability concurrently.If less than 0.1 parts by weight, just there is the tendency of solidified nature deterioration in addition, if surpass 5 parts by weight, the tendency that just exists storage stability to reduce.
In addition, in forming the pressure sensitive adhesive layer of adhesive sheet of the present invention, also can add and be used to the Photoepolymerizationinitiater initiater that causes radioactive rays polymerizable compound polymeric, generate free free radical by the irradiation of active light.As such Photoepolymerizationinitiater initiater, for example can use benzophenone, N, N '-tetramethyl--4,4 '-diaminobenzophenone (Michler's keton), N, N '-tetraethyl--4,4 '-diaminobenzophenone, 4-methoxyl group-4 '-the dimethylamino benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-methyl isophthalic acid-(4-(methylthio group) phenyl)-2-morpholino acetone-1,2,4-diethyl sulfenyl xanthone, 2-ethyl-anthraquinone, aromatic ketones such as phenanthrenequione, benzoin methyl ether, Benzoin ethyl ether, benzoin ethers such as st-yrax phenylate, benzoin methyl, st-yraxes such as ethyl st-yrax, benzyl derivatives such as benzyl dimethyl ketone acetal, 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(Chloro-O-Phenyl)-4,5-two (m-methoxyphenyl) imidazoles dimer, 2-(adjacent fluorophenyl)-4,5-phenylimidazole dimer, 2-(guaiacyl)-4,5-diphenyl-imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dimer, 2,4-two (p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, the 4-dimethoxy phenyl)-4,2 of 5-diphenyl-imidazole dimer etc., 4,5-triarylimidazoles dimer, the 9-phenylacridine, 1, the acridine derivatives of 7-two (9,9 '-acridyl) heptane etc. etc., they can use separately, perhaps can make up more than 2 kinds or 2 kinds and use.Usage quantity for above-mentioned Photoepolymerizationinitiater initiater has no particular limits, but the radioactive rays polymerizable compound of relative 100 parts by weight, preferably 0.01～30 parts by weight.
In addition, in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention,, also can add filler in order to improve its operability, improve thermal conductivity, adjust melt viscosity and to give thixotropy etc.As filler, have no particular limits, for example can enumerate aluminium hydroxide, magnesium hydroxide, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, aluminum oxide, aluminium nitride, aluminium borate whisker, boron nitride, crystallinity silicon-dioxide, amorphism silicon-dioxide etc., the shape of filler is had no particular limits.These fillers can use separately, perhaps can make up more than 2 kinds or 2 kinds and use.
Wherein, in order to improve thermal conductivity, preferential especially selective oxidation aluminium, aluminium nitride, boron nitride, crystallinity silicon-dioxide, amorphism silicon-dioxide etc.In addition, for the adjustment of melt viscosity or give thixotropic purpose, preferentially select aluminium hydroxide, magnesium hydroxide, lime carbonate, magnesiumcarbonate, Calucium Silicate powder, Magnesium Silicate q-agent, calcium oxide, magnesium oxide, crystallinity silicon-dioxide, amorphism silicon-dioxide etc.
The usage quantity of filler, the pressure sensitive adhesive layer of relative 100 parts by weight is preferably 1～20 parts by weight.If less than 1 parts by weight, just have the tendency that can not get additive effect, if surpass 20 parts by weight, with regard to existence cause that the storage modulus of binder layer rises, binding property reduces, by the tendency of the remaining problems such as electrical characteristic reduction that cause in space.
In addition, for the interface that makes storeroom of the same race not in conjunction with good, in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention, also can add various coupling agents.As coupling agent, for example can enumerate silane system, titanium system, aluminium system etc., on high this aspect of effect, be good especially with silane series coupling agent.
As above-mentioned silane series coupling agent, have no particular limits, for example can use vinyl trichloro silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, β-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan, N-β (aminoethyl) γ-aminopropyl methyl dimethoxysilane, γ-An Bingjisanyiyangjiguiwan, N-phenyl-γ-An Bingjisanjiayangjiguiwan, γ-mercaptopropyl trimethoxysilane, gamma-mercaptopropyltriethoxysilane, 3-aminopropyl methyldiethoxysilane, 3-urea propyl-triethoxysilicane, 3-urea propyl trimethoxy silicane, the 3-aminopropyl trimethoxysilane, 3-aminopropyl-three (2-methoxyl group-oxyethyl group) silane, N-methyl-3-aminopropyl trimethoxysilane, three aminopropyl trimethoxysilane, 3-4,5-dihydro imidazoles-1-base-propyl trimethoxy silicane, the 3-methacryloxypropyl trimethoxy silane, 3-mercapto propyl group methyl dimethoxysilane, the 3-chloropropylmethyldimethoxysilane, 3-chloropropyl dimethoxy silane, 3-cyanogen propyl-triethoxysilicane, hexamethyldisilazane, N, two (trimethyl silyl) ethanamides of O-, methyltrimethoxy silane, Union carbide A-162, ethyl trichlorosilane, the n-propyl Trimethoxy silane, the isobutyl-Trimethoxy silane, the amyl group trichlorosilane, octyltri-ethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, methyl three (iso-butylene acyl-oxygen base oxygen oxyethyl group) silane, methyl three (glycidyl oxygen base) silane, N-β (N-vinyl benzyl amino-ethyl)-γ-An Bingjisanjiayangjiguiwan, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, γ-chloropropyl dimethyl dichlorosilane (DMCS), gamma-chloropropylmethyldimethoxysilane, γ-chloropropyl methyldiethoxysilane, the trimethoxysilyl isocyanic ester, dimethoxy silyl isocyanic ester, methyl-silicane base triisocyanate, vinyl silyl triisocyanate, phenyl silyl triisocyanate, tetraisocyanate silane, Ethoxysilane isocyanic ester etc. can use separately or can make up more than 2 kinds or 2 kinds and to use.
In addition, as titanium is coupling agent, for example can use sec.-propyl trioctylphosphine titanic acid ester, sec.-propyl dimethyl propylene thiazolinyl isostearoyl titanic acid ester, sec.-propyl thirty dialkyl benzene sulphonyl titanic acid ester, isopropyl stearyl diallyl titanic acid ester, sec.-propyl three (dioctyl phosphoric acid ester) titanic acid ester, sec.-propyl three cumenyl phenyl titanium acid esters, sec.-propyl three (dioctylphyrophosphoric acid ester) titanic acid ester, sec.-propyl three (positive aminoethyl) titanic acid ester, two (dioctyl phosphorous acid ester) titanic acid ester of tetra isopropyl, two (two the tridecyl phosphorous acid esters) titanic acid ester of four octyl groups, four (2,2-diallyl oxygen ylmethyl-1-butyl) two (two tridecyls) phosphorous acid ester titanic acid ester, two cumenyl phenylium ester titanic acid ester, two (dioctylphyrophosphoric acid ester) fluoroacetic acid ester titanic acid ester, titanium isopropylate, tetra-n-butyl titanate, the butyl (tetra) titanate dimer, four (2-second hexyl) titanic acid ester, the acetopyruvic acid titanium, poly-acetopyruvic acid titanium, titanium octene oxyacetic acid, the titanium lactate ammonium salt, the lactic acid titanium, the titanium lactate ethyl ester, チ Application チ リ エ ノ Le ア ミ ネ-ト, poly-oxystearic acid titanium, positive metatitanic acid tetramethyl ester, positive tetraethyl titanate, positive metatitanic acid orthocarbonate, positive metatitanic acid four isobutyl esters, the stearyl titanic acid ester, metatitanic acid hydroxy toluene ester monomer, metatitanic acid hydroxy toluene ester polymer, diisopropoxy-two (2,4-diacetylmethane acid esters) titanium (IV), di-isopropyl-two-triethanolamine base titanic acid ester, octene titanium ethylene glycolate acid esters, four n-butoxy titanium polymers, three titanium n-butoxide monostearate ester polymers, three titanium n-butoxide monostearates etc. can use separately or can make up more than 2 kinds or 2 kinds and to use.
As aluminium is coupling agent, for example can use methyl aceto acetate aluminium diisopropyl acid esters, aluminium three (methyl aceto acetate), alkyl acetylacetic ester aluminium diisopropyl acid esters, aluminium one acetylacetic ester two (methyl aceto acetate), aluminium three (acetylacetic ester), aluminium-one isopropoxy one oily oxygen base methyl aceto acetate, aluminium-two n-butoxy one methyl aceto acetate, aluminium chelate compounds such as aluminium-diisopropoxy-a methyl aceto acetate, aluminium isopropylate, one tert.-butoxy diisopropyl acid aluminium, uncle's butyric acid aluminium, alkyd aluminium such as aluminum acetate can use separately or can make up more than 2 o'clock or 2 kinds and to use.
The usage quantity of above-mentioned coupling agent is from its effect or thermotolerance and the consideration of cost aspect, relative 100 parts by weight pressure sensitive adhesive layers, preferably 0.001～10 parts by weight.
For adsorbed ion impurity, insulating reliability when making moisture absorption improve, in the pressure sensitive adhesive layer that forms adhesive sheet of the present invention, can also add ion capturing agent.As such ion capturing agent, have no particular limits, for example can enumerate three azine mercaptan compounds, be that the copper poison of the stripping in order to prevent copper generation ionization of reductive agent etc. prevents agent and known compound, zirconium system, antimony bismuth are the mineral ion sorbent material of magnalium compound etc. etc. as bis-phenol.
The usage quantity of above-mentioned ion capturing agent is considered the pressure sensitive adhesive layer of relative 100 parts by weight, preferably 0.01～10 parts by weight from the effect or the aspects such as thermotolerance, cost that are produced by interpolation.
(storage modulus)
Form the pressure sensitive adhesive layer of adhesive sheet of the present invention, in the stage after being heating and curing, storage modulus is 10～2000MPa at 25 ℃ preferably, at 260 ℃ of 3～50MPa preferably.Storage modulus at 25 ℃ is more preferably 20～1900MPa, especially preferably 50～1800MPa.In addition, be more preferably 5～50MPa 260 ℃ storage moduluss, especially preferably 7～50MPa.If storage modulus is in this scope, just can guarantee by the difference of the thermal expansivity of semiconductor element and support and the thermal stresses that produces obtains the demulcent effect, with can suppress to peel off or when crackle took place, the operability of tackiness agent was good, can suppress the generation of reflowing crackle.Because the composition difference of pressure sensitive adhesive layer, the above-mentioned condition that is heating and curing are also different, but normally 120～240 ℃, 5～600 minutes scope.
This storage modulus, for example can use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4), the tackiness agent cured article is applied tension load, under the condition of frequency 10Hz, 5～10 ℃/min of heat-up rate, measure according to temperature dependency mensuration mode from-50 ℃ to 300 ℃ of mensuration.
The explanation of＜parameter 〉
Adhesive sheet of the present invention is to satisfy to have the sufficient adhesive that semiconductor element does not disperse when cutting, after this control bounding force between above-mentioned pressure sensitive adhesive layer and substrate layer by the irradiation radioactive rays, thereby when taking out, have the adhesive sheet of such phase cross-demand of the low bounding force that does not damage each element.Therefore, have with a slice film just can finish the cutting and such effect, the effect of each process of small pieces bonded.In addition, adhesive sheet of the present invention, have mounting semiconductor element with support member on desired thermotolerance and wet fastness during the big semiconductor element of encapsulation coefficient of thermal expansion differences.
In order further to seek to reach the optimizing of adhesive sheet of the present invention with such effect, effect, the inventor is from found that the viewpoint of characteristic or chemistry is studied, as described below, by predetermined parameter is carried out particular determination, then no matter the raw material that uses in adhesive sheet how, all obtains better above-mentioned action effect.
That is, the invention relates to adhesive sheet with regulation parameter.
At first, be purpose with the easy the present invention of understanding, the meaning of the parameter among the present invention is described.The determination object separately of the amount of flow among the present invention, melt viscosity and storage modulus is regarded pressure sensitive adhesive layer as.
Amount of flow in the present invention is mobile index, for example, is the size that adhesive sheet is cut into 10 * 20mm, be placed on the slide glass, at 160 ℃, with 0.8MPa pressurization 18 seconds, the length of overflowing around from the size at initial stage with light microscope determining and the value that obtains.
Bond strength in the present invention, only otherwise specify it is 90 ° of stripping strengths at above-mentioned pressure sensitive adhesive layer of expression and above-mentioned substrate layer interface.This bond strength, for example, be with above-mentioned adhesive sheet at room temperature or while heating the inside that is crimped on semiconductor wafer to be cut and after adhering to, only substrate layer measured with 90 ° of stretching angles, the peeling force of peeling off when draw speed 50mm/min stretches and the value that obtains.
Melt viscosity in the present invention is the index of film flowability, for example is to use parallel flat plastometer method to measure, the value that obtains by calculating.Melt viscosity for example is with 8 adhesive sheet laminations, makes the film of thick about 400 μ m, its stamping-out is become the circle of diameter 11.3mm, as sample, at 160 ℃, with load 2.5kgf pressurization 5 seconds, the thickness of the sample before and after the pressurization calculated with formula 1 described later.
Adhesion strength in the present invention, it is the index of the pressure-sensitive-adhesive of pressure sensitive adhesive layer, for example be to use RHESCA corporate system Star キ Application グ trier, peel off according to the method for putting down in writing among the JISZ0237-1991, at speed 10mm/s, contact load 100gf/cm 2, 1 second duration of contact condition under, measuring 25 ℃ of values of measuring and obtaining of temperature.
Tan δ (dielectric loss angle tangent) in the present invention, it is loss elastic modulus/storage modulus, belong to the energy dissipation item, it promptly is index in the flowability of this temperature, for example be to use the dynamic viscoelastic device, the value of measuring according to the condition of 5 ℃/min of heat-up rate, stretching mode, frequency 10Hz.
Storage modulus in the present invention is the index of the hardness (softness) of film, for example is to use the dynamic viscoelastic device, measures and the value that obtains with the condition of 5 ℃/min of heat-up rate, stretching mode, frequency 10Hz.
More than, done general introduction about the parameter of using among the present invention, but measuring method will be done suitably detailed explanation in the embodiment hurdle afterwards more specifically.
Below, enumerate several preferred forms of the present invention, and the meaning of the threshold value of parameter is described simultaneously.But the invention is not restricted to following mode.
(the 1st mode)
As a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer be above-mentioned pressure sensitive adhesive layer before (A1) radiation exposure and above-mentioned substrate layer interface bond strength for more than or equal to 200mN/cm and also (B1) amount of flow during 160 ℃ before radiation exposure be the adhesive sheet of 100～10000 μ m.
(the 2nd mode)
As another kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer be above-mentioned pressure sensitive adhesive layer before (A1) radiation exposure and above-mentioned substrate layer interface bond strength for more than or equal to 200mN/cm and also (B2) melt viscosity during 160 ℃ before radiation exposure be the adhesive sheet of 50～100000Pas.
In the adhesive sheet as a kind of mode of the present invention, the amount of flow of above-mentioned pressure sensitive adhesive layer is 100～10000 μ m before radiation exposure, and preferably 100～6000 μ m are more preferably 200～4000 μ m, most preferably are 500～4000 μ m.If amount of flow less than 100 μ m, just has on semiconductor wafer to be cut the possibility of bonding above-mentioned adhesive sheet fully,, the possibility of operation reduction such as operability is just arranged if surpass 10000 μ m.
In addition, in adhesive sheet as a kind of mode of the present invention, the ratio of the amount of flow before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer (irradiation back amount of flow/pre-irradiation amount of flow) is preferably more than or equal to 0.1, be more preferably more than or equal to 0.15, further preferably more than or equal to 0.2.If should the value less than 0.1, this in the engaging process of semiconductor element and support, the possibility that just has semiconductor element not engage fully.Though the maximum value of above-mentioned amount of flow ratio has no particular limits, common maximum value of getting is 1.0.
In adhesive sheet as a kind of mode of the present invention, the above-mentioned bond strength of (during cutting) before the radiation exposure, from when cutting in order to make unlikely this aspect consideration of dispersing of semiconductor element, preferably more than or equal to 200mN/cm, be more preferably more than or equal to 250mN/cm,, most preferably be further more than or equal to 350mN/cm preferably more than or equal to 300mN/cm.Because the bond strength height can prevent dispersing of semiconductor element, so the upper limit is had no particular limits, but from considering with the material and the suitable manufacturing process manufacturing that obtain easily, normally be less than or equal to 25000mN/cm, the material ratio that is less than or equal to 10000mN/cm is easier to make.
In addition, in adhesive sheet as a kind of mode of the present invention, to peel off the bond strength that peeling force obtains be to be less than or equal to 0.5 than (irradiation back bond strength/pre-irradiation bond strength) by above-mentioned 90 ° of the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, preferably being less than or equal to 0.4, most preferably is to be less than or equal to 0.3.If should be worth greater than 0.5, then when taking out, just have the tendency of each element of damage.On the other hand, the lower limit of above-mentioned bond strength than (irradiation back bond strength/pre-irradiation bond strength) had no particular limits, but for example from the viewpoint of operation, preferably more than or equal to 0.0001.
In addition, in adhesive sheet as a kind of mode of the present invention, to peel off the bond strength poor (pre-irradiation bond strength-irradiation is bond strength afterwards) that peeling force obtains be more than or equal to 100mN/cm by above-mentioned 90 ° of the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, more preferably be more than or equal to 150mN/cm, being more preferably more than or equal to 200mN/cm, most preferably is more than or equal to 250mN/cm.If should be worth less than 100mN/cm, when taking out, just have the tendency of each element of damage.
Adhesive sheet as a kind of mode of the present invention, amount of flow during by 160 ℃ before the radiation exposure that makes above-mentioned pressure sensitive adhesive layer reaches 100～10000 μ m, make 90 ° of preceding peeling forces of peeling off of radiation exposure more than or equal to 200mN/cm, making by the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure above-mentioned 90 °, to peel off the bond strength poor (pre-irradiation bond strength-irradiation is bond strength afterwards) that peeling force obtains be more than or equal to 100mN/cm, only pipe at low temperatures also can be on semiconductor wafer to be cut the above-mentioned adhesive sheet of crimping, can satisfy and when cutting, have enough bounding forces that semiconductor element does not disperse, and when taking out, have a such opposite characteristic of low bounding force of not damaging each element, therefore it is simultaneously very favorable to become on the technology cost, because the amount of flow before and after the radiation exposure reaches more than or equal to 0.1 than (irradiation back amount of flow-pre-irradiation amount of flow), therefore plays a role as the good adhesive sheet of joint reliability in the engaging process of semiconductor element and support member.
In addition, the melt viscosity when adhesive sheet of the present invention, before the radiation exposure of above-mentioned pressure sensitive adhesive layer 160 ℃ is 50～100000Pas, 50～10000Pas preferably, further 50～1000Pas preferably.If melt viscosity less than 50Pas, just exists on the semiconductor wafer to be cut the possibility of bonding above-mentioned adhesive sheet fully,, the possibility of operation reduction such as operability is just arranged if surpass 100000Pas.
In addition, in adhesive sheet as a kind of mode of the present invention, melt viscosity before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer is to be less than or equal to 100 than (irradiation back melt viscosity/pre-irradiation melt viscosity), is more preferably to be less than or equal to 95, further preferably is less than or equal to 90.If should value surpass 100, in the engaging process of semiconductor element and support member, just have semiconductor element bonded possibility fully.
In addition, adhesive sheet as a kind of mode of the present invention, melt viscosity during before the radiation exposure of above-mentioned pressure sensitive adhesive layer 160 ℃ is 50～100000Pas, making the preceding above-mentioned 90 ° of peeling forces peeled off of radiation exposure is more than or equal to 200mN/cm, making by the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure above-mentioned 90 ° again, to peel off the peeling force that obtains be more than or equal to 100mN/cm, although thus low temperature also can be on semiconductor wafer to be cut the above-mentioned adhesive sheet of crimping, can satisfy and when cutting, have enough bounding forces that semiconductor element does not disperse, and when taking out, have such opposite characteristic of the low bounding force that does not damage each element, therefore it is simultaneously very favorable to become on the technology cost, owing to the melt viscosity before and after the radiation exposure is reached more than or equal to 100 than (irradiation back melt viscosity/pre-irradiation melt viscosity), therefore in the engaging process of semiconductor element and support parts, plays a role as the good adhesive sheet of joint reliability.
(the 3rd mode)
In addition, as a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by radiation exposure, above-mentioned pressure sensitive adhesive layer be above-mentioned pressure sensitive adhesive layer before (A2) radiation exposure bond strength during by 25 ℃ of  5.1mm probe assay for more than or equal to 0.5N and also (B1) amount of flow during 160 ℃ before the radiation exposure be the adhesive sheet of 100～10000 μ m.
(the 4th mode)
In addition, as a kind of mode of the present invention, be to possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, the bond strength in the time of can enumerating above-mentioned pressure sensitive adhesive layer and be above-mentioned pressure sensitive adhesive layer before (A2) radiation exposure by 25 ℃ of  5.1mm probe assay for more than or equal to 0.5N and also (B2) melt viscosity during 160 ℃ before the radiation exposure be the adhesive sheet of 50～100000Pas.
Adhesive sheet as a kind of mode of the present invention, before the radiation exposure of above-mentioned pressure sensitive adhesive layer by 25 ℃ of  5.1mm probe assay the time bond strength be more than or equal to 0.5N, preferably more than or equal to 0.6N, being more preferably more than or equal to 0.7N, most preferably is more than or equal to 0.8N.If should be worth less than 0.5N the possibility that when cutting, just has semiconductor element to disperse.
In addition, adhesive sheet as a kind of mode of the present invention, adhesion strength poor (irradiation back adhesion strength-pre-irradiation adhesion strength) before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer during by 25 ℃ of  5.1mm probe assay is more than or equal to 0.1N, preferably, be more preferably more than or equal to 0.2N more than or equal to 0.15N.If should be worth less than 0.1N, when taking out, just have the tendency of each element of damage.
Under the situation of above-mentioned the 4th mode, in the engaging process of semiconductor element and support member, from semiconductor element bonded viewpoint preferably, in above-mentioned adhesive sheet, amount of flow before and after the radiation exposure than (irradiation back amount of flow/pre-irradiation amount of flow) preferably more than or equal to 0.1N, and the melt viscosity before and after the radiation exposure preferably is less than or equal to 100 than (irradiation back melt viscosity/pre-irradiation melt viscosity).
Adhesive sheet as a kind of mode of the present invention, amount of flow when making 160 ℃ before the radiation exposure of above-mentioned pressure sensitive adhesive layer reaches 100～10000 μ m, adhesion strength when making before the radiation exposure of above-mentioned pressure sensitive adhesive layer 25 ℃ by  5.1mm probe assay is more than or equal to 0.5N, adhesion strength poor (irradiation back adhesion strength-pre-irradiation adhesion strength) when making before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer 25 ℃ by  5.1mm probe assay is more than or equal to 0.1N, although thus low temperature also can be on semiconductor wafer to be cut the above-mentioned adhesive sheet of crimping, can satisfy and when cutting, have enough bounding forces that semiconductor element does not disperse, and when taking out, have an opposite like this characteristic of the low bounding force that does not damage each element, therefore it is simultaneously very favorable to become on the technology cost, because the amount of flow before and after the radiation exposure is more than or equal to 0.1 than (irradiation back amount of flow/pre-irradiation amount of flow), therefore plays a role as the good adhesive sheet of joint reliability in the engaging process of semiconductor element and support parts.
In addition, adhesive sheet as a kind of mode of the present invention, melt viscosity when making 160 ℃ before the radiation exposure of above-mentioned pressure sensitive adhesive layer is 50～100000Pas, make before the radiation exposure of above-mentioned pressure sensitive adhesive layer by 25 ℃ of  5.1mm probe assay the time adhesion strength be more than or equal to 0.5N, make before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer by 25 ℃ of  5.1mm probe assay the time adhesion strength poor (irradiation back adhesion strength-pre-irradiation adhesion strength) be more than or equal to 0.1N, although thus low temperature also can be on semiconductor wafer to be cut the above-mentioned adhesive sheet of crimping, can satisfy and when cutting, have enough bounding forces that semiconductor element does not disperse, and when taking out, have such opposite characteristic of the low bounding force that does not damage each element, therefore it is simultaneously very favorable to become on the technology cost, because the melt viscosity before and after the radiation exposure is to be less than or equal to 100 than (irradiation back melt viscosity/pre-irradiation melt viscosity), therefore plays a role as the good adhesive sheet of joint reliability in the engaging process of semiconductor element and support parts.
In addition, in above-described the 1st～the 4th mode, in order not damage each element when taking out, the above-mentioned bond strength behind the radiation exposure is preferably less than or equals 100mN/cm.But, on thicker semiconductor wafer, carry out when bonding, even also do not mind more than the 100mN/cm.What is called is less than or equal to 100mN/cm, is meant if below it, and no matter then can enumerate conduct is the value how thick semiconductor wafer (for example semiconductor wafer as thin as a wafer as thick 20 μ m) can both be suitable for.
As the method that the bond strength before the above-mentioned radiation exposure of pressure sensitive adhesive layer and adhesion strength are adjusted in desired scope, flowability in the time of can utilizing the room temperature that makes pressure-sensitive bonding agent layer rises, then bond strength and adhesion strength have the tendency that also rises, and make mobile the reduction, then bond strength and adhesion strength have the tendency that also reduces.For example, make the mobile occasion that rises, the content increase of softening agent, the methods such as content increase of giving bonding material are being arranged.Make the mobile occasion that reduces on the contrary, can reduce the content of above-claimed cpd.As above-mentioned softening agent, the so-called thinner that Acrylic Acid Monomer, monofunctional epoxy resin, liquid epoxy resin, acrylic resin, the epoxy that for example can enumerate simple function is etc.
In addition, the method of melt viscosity as the method for the amount of flow before the above-mentioned radiation exposure that improves pressure sensitive adhesive layer or before reducing above-mentioned radiation exposure, for example, can enumerate and add thinner, use the lower thermoplastic resin of Tg, use methods such as lower Resins, epoxy of Tg and solidifying agent.More particularly, use polyimide as the thermoplastic resin occasion, select acid mono and diamine monomer to reduce the imide concentration of polyimide, if synthesis of polyimides just can obtain the lower polyimide of Tg.In addition, using the occasion of acrylic rubber, or the carbon number of the alkyl by increasing the acrylic rubber side chain, or, all may reduce Tg by improving the bendability of main chain.
(the 5th mode)
In addition, as a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after (C1) radiation exposure poor (bond strength behind the bond strength-radiation exposure before the radiation exposure) for more than or equal to 100mN/cm, and (D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, tan δ during behind the radiation exposure 180 ℃ is the adhesive sheet more than or equal to 0.1.
(the 6th mode)
In addition, as a kind of mode of the present invention, be to possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after (C1) radiation exposure poor (bond strength behind the bond strength-radiation exposure before the radiation exposure) for more than or equal to 100mN/cm, and (D2) storage modulus during 120 ℃ before the radiation exposure for being less than or equal to 10MPa, storage modulus during behind the radiation exposure 180 ℃ is the adhesive sheet that is less than or equal to 100MPa.
In the above-mentioned the 5th and the 6th mode, viewpoint from the flowability that can control pressure sensitive adhesive layer, use has the adhesive sheet of characteristic (D1), on semiconductor wafer, has enough pressure sensitive adhesion power during the lamination adhesive sheet, have enough fusible viewpoints in the temperature of being less than or equal to 20 ℃ during from bonding semiconductor element, use adhesive sheet with characteristic (D2).In addition, in above-mentioned adhesive sheet, from have the viewpoint of good working concurrently in when cutting with when taking out, the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure is preferably less than than (bond strength before the bond strength/radiation exposure behind the radiation exposure) or equals 0.5.And, in above-mentioned adhesive sheet, from have the viewpoint of good working concurrently in when cutting with when taking out, preferably the bond strength before the radiation exposure on the interface of pressure sensitive adhesive layer and substrate layer is less than or equal to 200mN/cm, and the bond strength behind the radiation exposure is less than or equal to 100mN/cm.
In the adhesive sheet as a kind of mode of the present invention, the tan δ during 120 ℃ of the pressure sensitive adhesive layer before radiation exposure is more preferably more than or equal to 0.3 preferably more than or equal to 0.1.In addition, the tan δ 180 of the pressure sensitive adhesive layer behind the radiation exposure ℃ the time is preferably more than or equal to 0.1.If tan δ separately is less than 0.1, then the former the time, under any temperature of room temperature～150 ℃ by above-mentioned pressure sensitive adhesive layer on semiconductor wafer during the lamination adhesive sheet, can not guarantee has enough bounding forces to semiconductor wafer, in addition, when the latter, by pressure sensitive adhesive layer on the support parts during bonding semiconductor element, can not guarantee enough binding propertys being less than or equal under 200 ℃ the temperature.Like this,, just can make the flowability of the pressure sensitive adhesive layer under certain temperature carry out good the quantizing of precision by regulation tan δ, thus can control to the lamination of semiconductor wafer and small pieces after this in conjunction with the time necessary pressure sensitive adhesive layer flowability.
In addition, in above-mentioned adhesive sheet, the bond strength before the radiation exposure on the interface of pressure sensitive adhesive layer and substrate layer is more than or equal to 200mN/cm, preferably more than or equal to 250mN/cm, is more preferably more than or equal to 300mN/cm.If should be worth less than 200mN/cm the possibility that when cutting, just has semiconductor element to disperse.On the other hand, the above-mentioned bond strength behind the radiation exposure is preferably less than or equals 100mN/cm, if should be worth greater than 100mN/cm, just has the tendency of each element of damage when taking out.
And then, in above-mentioned adhesive sheet,,, can use with same reason with the identical value described in the 1st to the 4th mode for the bond strength difference and the bond strength ratio at the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure.
In addition, in adhesive sheet as a kind of mode of the present invention, storage modulus during before the radiation exposure of pressure sensitive adhesive layer 120 ℃ is to be less than or equal to 10PMa, be more preferably and be less than or equal to 5PMa, further preferably be less than or equal to 2PMa, storage modulus during behind the radiation exposure 180 ℃ is to be less than or equal to 100PMa, is more preferably to be less than or equal to 50PMa, further preferably is less than or equal to 10PMa.The former the time, if storage modulus greater than 10PMa, then under any temperature of room temperature～150 ℃ by above-mentioned pressure sensitive adhesive layer on semiconductor wafer during the lamination adhesive sheet, just can not guarantee has enough bounding forces to semiconductor wafer.In addition, when the latter, if storage modulus greater than 100PMa, then by pressure sensitive adhesive layer on support member during bonding semiconductor element, just can not guarantee enough binding propertys being less than or equal under 200 ℃ the temperature.
(the 7th mode)
In addition, as a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, adhesion strength when above-mentioned pressure sensitive adhesive layer is 25 ℃ of pressure sensitive adhesive layer before and after (C2) radiation exposure poor (adhesion strengths during behind the adhesion strength-radiation exposure during before the radiation exposure 25 ℃ 25 ℃) is more than or equal to 0.1N/  5.1mm probe, and (D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, and the tan δ during behind the radiation exposure 180 ℃ is the adhesive sheet more than or equal to 0.1.
(the 8th mode)
In addition, in a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, adhesion strength when above-mentioned pressure sensitive adhesive layer is 25 ℃ of pressure sensitive adhesive layer before and after (C2) radiation exposure poor (adhesion strengths during behind the adhesion strength-radiation exposure during before the radiation exposure 25 ℃ 25 ℃) is more than or equal to 0.1N/  5.1mm probe, and (D2) storage modulus during 120 ℃ before the radiation exposure is to be less than or equal to 10MPa, and the storage modulus during behind the radiation exposure 180 ℃ is the adhesive sheet that is less than or equal to 100MPa.
In the above-mentioned the 7th and the 8th mode, viewpoint from the flowability that can control pressure sensitive adhesive layer, use has the adhesive sheet of characteristic (D1), have the viewpoint of enough bounding forces in the temperature of being less than or equal to 20 ℃ when having enough pressure sensitive adhesion power, bonding semiconductor element when adhesive sheet is laminated to semiconductor wafer, use adhesive sheet with characteristic (D2).In addition, in above-mentioned adhesive sheet, from have the more viewpoint of good working concurrently in when cutting with when taking out, in above-mentioned adhesive sheet, preferably the bond strength before the radiation exposure on the interface of pressure sensitive adhesive layer and substrate layer is more than or equal to 200mN/cm, and the above-mentioned bond strength behind the radiation exposure is less than or equal to 100mN/cm.
In addition, in above-mentioned adhesive sheet, adhesion strength during 25 ℃ of the pressure sensitive adhesive layer behind the radiation exposure poor (adhesion strengths during before the adhesion strength-radiation exposure during before the radiation exposure 25 ℃ 25 ℃), consider from can under the condition of not damaging each element, taking out this point, being feature more than or equal to 0.1N/  5.1mm probe, preferably, be more preferably probe more than or equal to 0.2N/  5.1mm more than or equal to 0.15N/  5.1mm probe.
In addition, in above-mentioned adhesive sheet, adhesion strength during 25 ℃ of the pressure sensitive adhesive layer before the radiation exposure is preferably more than or equal to 0.5N/  5.1mm probe, and the adhesion strength during 25 ℃ of the pressure sensitive adhesive layer behind the radiation exposure is preferably more than or equal to 0.4N/  5.1mm probe.If the adhesion strength during 25 ℃ of the pressure sensitive adhesive layer before the radiation exposure is less than 0.5N/  5.1mm probe, the possibility that when cutting, just has semiconductor element to disperse.On the other hand, if just there is the tendency of above-mentioned each element in the bond strength during 25 ℃ of the pressure sensitive adhesive layer behind the radiation exposure greater than 0.4N/  5.1mm probe when taking out.
In addition, in above-described the 5th～the 8th mode, the above-mentioned bond strength of (during cutting) before the radiation exposure, from on when cutting, semiconductor element can not disperse this aspect, preferably more than or equal to 200mN/cm, being more preferably more than or equal to 250mN/cm, further preferably more than or equal to 300mN/cm, most preferably is more than or equal to 350mN/cm.Because the high person of bond strength can prevent dispersing of semiconductor element, so the upper limit is had no particular limits, but, be easier to make and be less than or equal to the 10000mN/cm ratio from can normally being less than or equal to 25000mN/cm with what suitable manufacture method was made with the material that obtains easily.In addition, in order not damage each element when taking out, the above-mentioned bond strength before and after the radiation exposure is preferably less than or equals 100mN/cm.But, on thicker semiconductor wafer, carry out the adherent occasion, even also do not mind more than the 100mN/cm.What is called is less than or equal to 100mN/cm, is meant if below it, and no matter then can enumerate conduct is the value how thick semiconductor wafer (for example semiconductor wafer as thin as a wafer as thick 20 μ m) can both be suitable for.
Method that bond strength difference before and after above-mentioned as making (C1) radiation exposure increases or the method that the adhesion strength difference before and after above-mentioned (C2) radiation exposure is increased, for example with thermoplastic resin, thermosetting resin with pass through in the pressure sensitive adhesive layer of compound that radiation exposure produces base, just can reach by the usage ratio that increases heat reactive resin and produce the compound of base as neccessary composition.But, if make above-mentioned bond strength difference and adhesion strength difference big, just there are the amount of flow ratio of above-mentioned radiation exposure front and back and the tendency that the melt viscosity ratio increases simultaneously, therefore are preferably on the acquisition equilibrated basis, determine the usage ratio of heat reactive resin and the compound that produces base.
The method that tan δ during behind tan δ during as make before the above-mentioned radiation exposure 120 ℃ and the radiation exposure 180 ℃ rises or make radiation exposure before 120 ℃ the time storage modulus and the method that reduces of the storage modulus behind the radiation exposure, as long as use the flowability of pressure sensitive adhesive layer such known method that rises just passable.Specifically, for example can enumerate and add thinner, use the lower thermoplastic resin of Tg or use low thermosetting resin of Tg and solidifying agent etc.As all Tg of pressure sensitive adhesive layer, if, so after this just carry out optimizing easily behind radiation exposure by selecting material to make before radiation exposure to be 120 ℃ of front and back, be 180 ℃ of front and back.
(the 9th mode)
In addition, as a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is when uncured or semi-cured state, storage modulus under 50 ℃ is more than or equal to 0.1MPa, be less than or equal to 200MPa, storage modulus 50 ℃ under is more than or equal to pre-irradiation 2 times behind a certain amount of radioactive rays of irradiation, and the amount of flow under after shining a certain amount of radioactive rays 160 ℃ is more than or equal to 100 μ m, the adhesive sheet that is less than or equal to 10000 μ m.
(the 10th mode)
In addition, as a kind of mode of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is in uncured or semi-cured state, storage modulus under 50 ℃ is more than or equal to 0.1MPa, be less than or equal to 200MPa, storage modulus under 50 ℃ is more than or equal to pre-irradiation 2 times behind a certain amount of radioactive rays of irradiation, and the melt viscosity under 160 ℃ is more than or equal to 50Pas, the adhesive sheet that is less than or equal to 106Pas.
(the 11st mode)
In addition, as a kind of mode of the present invention, can enumerate the adhesive sheet that possesses pressure sensitive adhesive layer and substrate layer, controls the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is more than or equal to 0.1MPa, is less than or equal to 200MPa in uncured or semi-cured state, storage modulus under 50 ℃, storage modulus under 50 ℃ is more than or equal to pre-irradiation 2 times behind a certain amount of radioactive rays of irradiation, and the storage modulus under 180 ℃ is the adhesive sheet that is less than or equal to 100MPa.
In the adhesive sheet of above-mentioned the 9th, the 10th and the 11st mode, storage modulus under 50 ℃ of the adhesive sheet of uncured or semi-cured state is that 0.1～200MPa is necessary, preferably 0.5～150MPa is more preferably 1.0～100MPa, especially preferably 2～50MPa.If the breakage of semiconductor element etc. less than 0.1MPa, when cutting, just takes place in storage modulus easily, is improper therefore.If surpass 200MPa, just can not with the wafer lamination, be improper therefore, and in the scope of 2～50MPa, from cutting, and the plyability of wafer on all be best.
In addition, shining storage modulus under 50 ℃ of adhesive sheet behind a certain amount of radioactive rays is that more than or equal to pre-irradiation 2 times are necessary.If less than 2 times, then be difficult to peel off owing to semiconductor element behind the radiation exposure from base material film, be improper therefore.Can easily peel off this point from slim semiconductor element etc. and consider, then be preferably more than or equal 4 times, be preferably more than especially or equal 10 times from base material film.
In the adhesive sheet of a kind of mode of the present invention, the amount of flow under 160 ℃ of the adhesive sheet of irradiation behind a certain amount of radioactive rays on the adhesive sheet of uncured or semi-cured state is being necessary more than or equal to 100 μ m, the scope that is less than or equal to 10000 μ m.Under the situation of amount of flow less than 100 μ m, flowability and wettability are not enough when the crimping of semiconductor element, and binding property reduces, thereby is worthless.In addition, surpass under the situation of 10000 μ m in amount of flow, when the crimping of semiconductor element, flow out from the end of semiconductor element owing to resin superfluously, cover the electrode terminal section of the support member of semiconductor element, it is difficult that processes such as wire bonding become, in addition, because the thickness of adhesive sheet reduces, so binding property reduces, thereby be not good.
At resin from the outflow of semiconductor element end on bright littler this aspect, amount of flow preferably more than or equal to 100 μ m, be less than or equal to the scope of 6000 μ m.In addition, as the support member of semiconductor element, under the situation of the substrate on band that uses charged road or charged road, the circuit fillibility increase and also at resin from the outflow of end on littler this aspect, amount of flow is the scope of 1000 μ m～4000 μ m preferably.
When the amount of flow B behind a certain amount of radioactive rays of irradiation satisfies concerning of B/A 〉=1/10 at the amount of flow A under 160 ℃ of the adhesive sheet of uncured or semi-cured state with on this adhesive sheet, even the deviation of radiation exposure amount or condition reaches to a certain degree, the deviation of the amount of flow behind the radiation exposure is also few, is preferably therefore.In addition, for the deviation that makes the amount of flow behind radiation exposure still less, further preferred B/A 〉=1/5 most preferably is B/A 〉=1/2.
In the adhesive sheet of a kind of mode of the present invention, the melt viscosity under 160 ℃ behind a certain amount of radioactive rays of irradiation on the pressure sensitive adhesive layer is that 50～100000Pas is necessary.During less than 50Pas, mobile excessive at melt viscosity, effusive resin becomes many from the end, in addition, because this, in order to reduce the thickness of adhesive sheet, the tendency that just exists binding property to reduce.In addition, when surpassing 100000Pas, the mobile reduction, the tendency that exists binding property or circuit fillibility to reduce.
In addition, storage modulus under 50 ℃ behind a certain amount of radioactive rays of irradiation on the adhesive sheet of uncured or semi-cured state is if more than or equal to 15MPa, and then this is particularly preferred for can easily peel off the next institute of slim semiconductor element from substrate film.
And then, under low temperature, can consider by lamination, storage modulus under 100 ℃ of the adhesive sheet of uncured or semi-cured state is 0.0001～2MPa, from cutting easy consideration, storage modulus under 50 ℃ is 0.1～200MPa, from peeling off easy consideration, storage modulus under behind the radiation exposure 50 ℃ is 15～200MPa, from mobile high consideration, storage modulus under 180 ℃ preferably is less than or equal to 100MPa, in addition, consider that the storage modulus under back 50 ℃ of curing is 100～5000MPa especially preferably at good heat resistance.Storage modulus during 50 ℃ of the adhesive sheet of above-mentioned uncured or semi-cured state, further from the good consideration of cutting operation, preferably 5～100MPa is more preferably 7.5～50MPa.
In the adhesive sheet of a kind of mode of the present invention, in the stage that pressure sensitive adhesive layer has been heating and curing, storage modulus is at 25 ℃ of 10～2000MPa preferably, at 260 ℃ of 3～50MPa preferably.Storage modulus under 25 ℃ is more preferably 20～1900MPa, especially preferably 50～1800MPa.In addition, the storage modulus under 260 ℃ is more preferably 4～50MPa, especially preferably 5～50MPa.If storage modulus is in this scope, just guarantee to make the thermal stresses demulcent effect that produces by the coefficient of thermal expansion differences of semiconductor element and support member, can suppress to peel off or the generation of crackle, simultaneously can control the operability of tackiness agent, the thickness and precision of binder layer, and the generation that suppresses the reflowing crackle.
Can be by for example increasing the usage quantity of Resins, epoxy in the storage modulus of the pressure sensitive adhesive layer in the above-mentioned stage that has been heating and curing, or use high Resins, epoxy of glycidyl concentration or the high resol of hydroxyl concentration to wait to improve all cross-linking densities of polymkeric substance and be increased.If adopt and above-mentioned opposite means, storage modulus is worthwhile so can not to be reduced yet.
In the adhesive sheet of a kind of mode of the present invention, by the pressure sensitive adhesive layer of the adhesive sheet behind the radiation exposure, the bond strength (stripping strength) under 250 ℃ of the lamination cured article of bonding 5mm quadrate semiconductor element and support member is preferably more than or equal to the 3.0N/ sheet.As the side of peeling off between semiconductor element and support member, roughly be divided into the interfacial failure between pressure sensitive adhesive layer and support member, peeled off and pressure sensitive adhesive damage layer and the aggegation of peeling off destroys.In order to suppress interfacial failure, or the flowability of raising pressure sensitive adhesive layer, or the skill and technique of the amount of flow of the pressure sensitive adhesive layer behind the raising radiation exposure is effective, destroy in order to suppress aggegation, selecting material is effective so that the cross-linking density of pressure sensitive adhesive layer uprises, improves molecular weight, the Young's modulus when making 260 ℃ of thermoplastic resin in the skill and technique such as scope of 0.01～50MPa.
As previously discussed, be described though enumerate several concrete modes, above-mentioned various characteristics is for obtaining the effective characteristic of better adhesive sheet, therefore by the above-mentioned various characteristics of appropriate combination, can accessing more good adhesive sheet certainly.
(adjustment of degree of cure)
Adhesive sheet as a kind of mode of the present invention, in pressure sensitive adhesive layer, contain with thermoplastic resin and thermosetting resin occasion as the adhesive sheet of principal constituent, the thermal value that is recorded by DSC (differential scanning calorimeter) that is located at the pressure sensitive adhesive layer when having shone radioactive rays on the above-mentioned adhesive sheet is A, when the thermal value before the radiation exposure is B, preferably has the formation of (B-A)/B=0.1～0.7.
In above-mentioned adhesive sheet, the thermal value that is recorded by DSC of establishing the pressure sensitive adhesive layer when having shone radioactive rays is A, and when the thermal value before the radiation exposure was B, preferably (B-A)/B=0.1～0.7 was more preferably 0.2～0.5.During for the taking-up behind radiation exposure semiconductor element is not caused damage, preferably more than or equal to 0.1.In addition, after taking-up, when being combined in the semiconductor element heating on the support member, in order to ensure sufficient flowability, preferably more than or equal to 0.7 by pressure sensitive adhesive layer.
The so-called thermal value that records by above-mentioned DSC, as illustrated in evaluation method described later hurdle, be to use differential scanning calorimeter (being called " DSC " in this manual), the value of obtaining when measuring with the condition of 10 ℃/minute of heat-up rates, 20 ℃～300 ℃ of mensuration temperature.
In addition, promote that in above-mentioned pressure sensitive adhesive layer, to contain the photoreactive compound of the curing reaction of heat reactive resin is a feature by radiation exposure.Be that the compound that radiation exposure by wavelength 150～750nm produces base is a feature also with above-mentioned photoreactive compound.
Produce the compound of base by above-mentioned radiation exposure,, just be not particularly limited so long as produce the compound of base through radiation exposure.As the base that produces, consider from reactive, curing speed aspect, preferably the strong-base group compound.In general, as the index of base, use be the logarithm pKa value of acid dissociation constant, preferably the pKa value in the aqueous solution is the base more than or equal to 7, is more preferably the base more than or equal to 9.The example that employed smooth base produces agent is as discussed previously.
In above-mentioned adhesive sheet, the Tg of employed thermoplastic resin is-50～10 ℃, and weight-average molecular weight is 100000～1000000.If Tg is lower than-50 ℃, can lose self-supporting as pressure sensitive adhesive layer, on operability, have problems, if Tg surpasses 10 ℃, needed temperature just uprises when bonding, all is worthless.(moreover, the Tg among the present invention, illustrated in the hurdle as afterwards evaluation method, the value that expression uses DSC to measure.) in addition, if weight-average molecular weight in this scope, intensity, flexibility and tackiness when forming laminar or film like are suitable, in addition because mobile suitably, so can guarantee the good circuit fillibility of distribution.If weight-average molecular weight beyond above-mentioned scope, can be damaged the above-mentioned characteristic when forming laminar or film like, be worthless therefore.Moreover, in the present invention, so-called weight-average molecular weight, illustrated in the hurdle as afterwards evaluation method, expression is measured with gel permeation chromatography (also being called " GPC " in this manual), the value that use polystyrene standard measuring line converts.
In addition, in above-mentioned adhesive sheet, the Tg of employed thermoplastic resin is 10～100 ℃, and weight-average molecular weight is 5000～20000.About above-mentioned Tg, be more preferably 10～80 ℃.If Tg is lower than 10 ℃, can lose self-supporting as pressure sensitive adhesive layer, on operability, have problems, if Tg surpasses 100 ℃, needed temperature just uprises when bonding, all is worthless.Moreover, the Tg among the present invention, the value that expression is obtained according to DSC.In addition,, be more preferably 20000～150000, further preferably 20000～80000 about above-mentioned weight-average molecular weight.If weight-average molecular weight is in this scope, intensity, flexibility and binding property when forming laminar or film like are suitable, in addition, since suitably mobile, so can guarantee the good circuit fillibility of distribution.If weight-average molecular weight beyond above-mentioned scope, can be damaged the above-mentioned characteristic when forming laminar or film like, be worthless therefore.Moreover, so-called above-mentioned weight-average molecular weight, expression is measured with gel permeation chromatography, the value of using the polystyrene standard measuring line to convert.
(chemical structure of pressure sensitive adhesive layer)
For to have the above-mentioned effect that can simplify flow chart, the adhesive sheet of the present invention of effect is done further optimization, the inventor is from found that the side of the chemical structure of pressure sensitive adhesive layer is studied, pressure sensitive adhesive layer by formation has the following illustrated characteristic of picture just can obtain above-mentioned action effect better.
Promptly, as the adhesive sheet of a kind of mode of the present invention and the resin combination of this adhesive sheet of formation, preferably to the island that does not have a cross-linked structure before radiation exposure and the heating resin that is separated, have the island phase that constitutes by the resin that forms cross-linked structure and do not form cross-linked structure by radiation exposure but form the marine facies that the resin of crosslinking structure constitutes by heating by radiation exposure.
In order to give the binding property in the B step state, preferably do not have cross-linked structure before the radiation exposure.And then the result who has studied the molecular structure behind the radiation exposure is clear, forms cancellated occasion at marine facies, there be mobile the reduction, the tendency that binding property reduces, in addition, mutually do not form cancellated occasion on the island, have the high and tendency that becomes and be difficult for peeling off of binding property.That is, when adhesive sheet had been shone radioactive rays, on this aspect of binding property, preferred island formed cross-linked structure mutually, and on the other hand, on this aspect of easy release adhesive layer from substrate layer, preferred marine facies do not form cross-linked structure.
At radiation exposure with after being heating and curing, marine facies, island all have cross-linked structure mutually, are necessary giving on the thermotolerance.About island structure, sample section is carried out scanning electronic microscope (SEM) observe, judge that dispersive partly is the island phase, successive partly is the island phase.About radiation exposure amount and wavelength, it is adjusted to produces above-mentioned effect.
In addition, the formation of the cross-linked structure of each phase is concluded as following.That is, test portion (weight Xg) in 10gMEK, 25 ℃ soak into 1 hour after, remove insolubles with 200 purpose nylon cloths.Measure its filtrate (solvent components) by the weight Y under 170 ℃, after dry 1 hour, from weight ratio Y/X * 100 (%) of initial stage test portion, determine solvent components ratio (%).Less than 80% o'clock,, conclude that marine facies form cross-linked structure at the solvent components ratio from forming reticulated structure, forming insoluble part.In addition, be more than or equal to 80% o'clock at the solvent components ratio, the visible light transmissivity with the thick mesh of 5mm of filtrate is more than or equal to 80%, concludes that marine facies, island all have cross-linked structure mutually.Filtrate with the thick netted visible light transmissivity of 5mm less than 80%, conclude that marine facies have cross-linked structure, but the island does not have cross-linked structure mutually.
Pass through radiation exposure, the resin combination that has the island structure of above-mentioned characteristic as formation, for example can enumerate the combination of high molecular weight components in the early stage and the lower molecular weight thermofixation composition that mixes, wherein, from thermotolerance, the good consideration of binding property, preferably contain (methyl) acrylic copolymer of glycidyl and the combination of Resins, epoxy.
To peel off the bond strength that peeling force obtains be to be less than or equal to 0.5 than (bond strength of postradiation bond strength/pre-irradiation) by above-mentioned 90 ° of the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, being more preferably and being less than or equal to 0.4, most preferably is to be less than or equal to 0.3.If should be worth greater than 0.5, when taking out, just have the tendency of each element of damage.On the other hand, above-mentioned bond strength has no particular limits than the lower limit of (bond strength of postradiation bond strength/pre-irradiation), but for example from the viewpoint of operation, preferably more than or equal to 0.0001.Have again, the bounding force at the above-mentioned pressure sensitive adhesive layer of (before the radiation exposure) and above-mentioned substrate layer interface during cutting, can be after adhering to above-mentioned adhesive sheet in room temperature or while heating crimping on the semiconductor wafer to be cut, only substrate layer is measured with 90 ° of stretching angles, the peeling force of peeling off when draw speed 50mm/min stretches.
In addition, in above-mentioned adhesive sheet, to peel off the bond strength poor (pre-irradiation bond strength-irradiation is bond strength afterwards) that peeling force obtains be more than or equal to 100mN/cm by above-mentioned 90 ° of the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, more preferably be more than or equal to 150mN/cm,, most preferably be further more than or equal to 250mN/cm preferably more than or equal to 200mN/cm.If should be worth less than 100mN/cm, when taking out, just have the tendency of each element of damage.
Amount of flow on the adhesive sheet of uncured or semi-cured state 160 ℃ of the adhesive sheet of irradiation behind a certain amount of radioactive rays the time is preferably in the scope more than or equal to 100 μ m, 10000 μ m.
＜manufacture method 〉
Adhesive sheet of the present invention can be by will forming adhesive sheet group and thing dissolving or be dispersed in and form varnish in the solvent, coating on substrate film, add the heat extraction solvent and obtain.
Adhesive sheet of the present invention is after cutting process is ended, the active ray that irradiation has the wavelength region of 150～750nm to adhesive sheet, make adhesive sheet polymerizing curable with radioactive rays polymerizability, reduce the bounding force at adhesive sheet and ground interface, make the taking-up of semiconductor element become possible adhesive sheet.
In addition, as the solvent that is used for above-mentioned varnishization, have no particular limits, if but the volatility when considering that film is made etc. are for example preferably used the lower solvents of boiling point such as methyl alcohol, ethanol, 2-methyl cellosolve, cellosolvo, butoxy ethanol, methylethylketone, acetone, methyl isopropyl Ketone, toluene, dimethylbenzene.In addition, be purpose with filming property of raising etc., for example also can use the higher solvents of boiling point such as N,N-DIMETHYLACETAMIDE, dimethyl formamide, N-Methyl pyrrolidone, pimelinketone.These solvents can use separately, perhaps also can make up more than 2 kinds or 2 kinds and use.
Make for the varnish when adding mineral filler, consider the dispersiveness of mineral filler, preferably use sand mill, 3 roller machines, ball mill and bead grinding machine etc., in addition, also they can be used in combination.In addition, with after mineral filler and the mixing of low-molecular-weight raw material,, also can shorten the blended time in advance by cooperating the high-molecular weight raw material.In addition, form varnish after, also can remove bubble in the varnish by vacuum outgas etc.
As method to substrate film coating varnish, can use known method, for example can enumerate scraper coating method, roller coating method, spraying method, engraved roll coating method, the excellent spread coating that winds the line, curtain coating method etc.
Thickness to adhesive sheet has no particular limits, but pressure sensitive adhesive layer, substrate layer preferably all are 5～250 μ m.If thinner than 5 μ m, as just to exist the stress alleviation effects to lack tendency, if thicker than 250 μ m, not only uneconomical, and could not adapt to the requirement of the miniaturization of semiconductor element.
In addition, adhesive sheet of the present invention in order to obtain desired sheet thickness, also can be designed at the binder layer or the pressure sensitive adhesive layer that sandwich between semiconductor wafer and the pressure sensitive adhesive layer more than 1 layer or 2 layers again.In this occasion,, except the pressure sensitive adhesive layer that is prepared into above-mentioned method, also can use the pressure sensitive adhesive layer that is prepared into known method in the past as the pressure sensitive adhesive layer that is provided with according to above-mentioned requirements.As the pressure sensitive adhesive layer that is provided with according to above-mentioned requirements, can use the commercial adhesive sheet that can buy, for example polyimide system, the oligomeric system of silicon, rubber-epoxy system, epoxy are tackiness agent.But,, need to consider that pressure sensitive adhesive layer does not take place peels off such laminating condition mutually based on technique known in the past.
＜using method 〉
If shine radioactive rays on the adhesive sheet that has as the formation of above explanation, pressure sensitive adhesive layer just reduces greatly to the bounding force of substrate layer behind radiation exposure.Therefore, as illustrated later on, in the cutting process when making semiconductor element, owing to use adhesive sheet of the present invention, pressure sensitive adhesive layer and substrate layer just become and peel off easily, and the result can take out the semiconductor element of the pressure sensitive adhesive layer of having fitted better.
Zhao She radioactive rays are the active rays with 150～750nm wavelength in the present invention, and ultraviolet ray, far ultraviolet rays yue, near-ultraviolet ray, visible rays, electron beam, infrared rays, near infrared ray etc. are arranged.For example can use Cooper-Hewitt lamp, middle medium pressure mercury lamp, high pressure mercury vapour lamp, extra-high-pressure mercury vapour lamp, xenon lamp, metal halide lamp, carry out 0.01～10000J/cm 2Irradiation.
By above-mentioned radiation exposure, solidify owing to be included in the part of the thermopolymerization resin in the pressure sensitive adhesive layer, think that therefore the bounding force between pressure sensitive adhesive layer and substrate layer reduces.When only can not get the reduction of sufficient adhesive, preferably by also promoting curing reaction with heating by above-mentioned radiation exposure.As the temperature of above-mentioned heating, should be according to the situation of carrying out of the curing reaction that produces by radiation exposure, also different in addition because the composition of pressure sensitive adhesive layer is different, but adhesive sheet can be exposed in 30～100 ℃ the atmosphere usually.Above-mentioned heating can be used well heater or baking oven, but general radiation exposure source, it is many to generate heat when radiation exposure, if utilize this heating, does not just need to prepare in addition heating unit, is desirable therefore.
In addition, the bounding force at above-mentioned pressure sensitive adhesive layer behind the radiation exposure of the present invention and above-mentioned substrate layer interface, for example behind the above-mentioned adhesive sheet of fitting in room temperature or while heating crimping on the semiconductor wafer to be cut, when only substrate layer being stretched with 90 ° of stretching angles, draw speed 50mm/min to peel off peeling force (bond strength) be to be less than or equal to 100mN/cm, be more preferably more than or equal to 90mN/cm, further preferably more than or equal to 80mN/cm.If should value surpass 100mN/cm, when taking out, just have the tendency of each element of damage.
Then, with reference to Fig. 1～Fig. 8, the using method of relevant adhesive sheet of the present invention is described, but using method of the present invention is not limited to following method.Moreover, to the identical symbolic representation of usefulness that has identical function among the figure, omit its explanation.
The adhesive sheet 10 that possesses substrate film 1 and the 1st pressure sensitive adhesive layer 2 shown in Figure 1, shown in Figure 2 except that above-mentioned formation prerequisite, also possess the adhesive sheet 20 of pressure sensitive adhesive layer 3.
With these adhesive sheets 10,20 as the occasion that dicing tape uses, at first, adhesive sheet 10,20 is positioned on the operation post of regulation, make above-mentioned pressure sensitive adhesive layer 2,3 and wafer surface adherence.
Moreover, on adhesive sheet of the present invention, be provided with under the situation of separability thin slice, after peeling off this separability thin slice of removal, the above-mentioned pressure sensitive adhesive layer 2,3 of adhesive sheet is positioned on the operation post of regulation up.
Then, as shown in Figure 3, the semiconductor wafer A of adhesion processing to be cut on the 2nd pressure sensitive adhesive layer 3.At this moment, as previously mentioned,, also binder layer or pressure sensitive adhesive layer more than 1 layer or 2 layers can be set again, insert it between semiconductor wafer A and the 2nd pressure sensitive adhesive layer 3 in order to obtain desired sheet thickness.
Then, in this adherence state, on semiconductor wafer A, apply cutting, clean, exsiccant process.At this moment, because semiconductor wafer A utilizes the 2nd pressure sensitive adhesive layer 3 to adhere fully and is attached on the adhesive sheet, therefore do not come off at above-mentioned each interprocedual semiconductor wafer A.
In Fig. 4, use small pieces cutting machine 6 again, wafer A is cut out the otch of representing with thick line, obtain semiconductor element A1, A2, A3.
Then, as shown in Figure 5,, make a part or most of polymerizing curable of adhesive sheet with radioactive rays polymerizability to pressure sensitive adhesive layer 2, the 3 irradiation radioactive rays B of adhesive sheet.At this moment, in order to promote curing reaction simultaneously or behind the radiation exposure, also can and use heating at radiation exposure.By and with heating, can reduce bounding force in the short period of time at low temperature more.Heating temperature is not so long as below the heat decomposition temperature of pressure sensitive adhesive layer, just be subjected to limit especially, but preferentially select 50～170 ℃ temperature.
The radiation exposure that carries out to adhesive sheet is shown in arrow B among Fig. 5, from that face incident that pressure sensitive adhesive layer 2 is not set of substrate film 1.As previously mentioned, when the occasion of using UV (ultraviolet ray) as radioactive rays, substrate film 1 must have photopermeability, but uses the occasion of EB (electron beam) as radioactive rays, and substrate film 1 not necessarily must have photopermeability.
Behind the radiation exposure, as shown in Figure 6, for example by attracting opening chuck 4 that semiconductor element A1, A2 to be removed, A3 are taken out.At this moment, need not attract opening chuck 4 or simultaneously and attract opening chuck 4 and usefulness, for example utilize shank etc. also can make semiconductor element A1, A2 to be removed, A3 projection below substrate film 1.
The bounding force that semiconductor element A1 and pressure sensitive adhesive layer are 3, bounding force than 1 of pressure sensitive adhesive layer 2 and substrate film is big, in case take out semiconductor element A1, then pressure sensitive adhesive layer 2 is peeled off (with reference to Fig. 7) with the following state attached to semiconductor element A1.
Then, semiconductor element A1, A2, A3 are positioned in mounting semiconductor element with heating on the support member 5 by pressure sensitive adhesive layer 2.By heating, pressure sensitive adhesive layer 2 shows bounding force, finishes semiconductor element A1, A2, A3 and mounting semiconductor element bonding (with reference to Fig. 8) with support member 5.
Above Shuo Ming adhesive sheet of the present invention, be after cutting process finishes, to adhesive sheet irradiation ultraviolet radiation (UV) or electron beam (EB) isoradial, make adhesive sheet carry out polymerizing curable with radioactive rays polymerizability, reduce the bounding force at tackiness agent (layer) and substrate film interface, make the taking-up of semiconductor element become possibility.Under the situation of in the past adhesive sheet, if the surface tension of ground surpasses 40mN/m, then the reduction of the bounding force at adhesive sheet and ground interface is insufficient, has the tendency of taking out the property deterioration.But, adhesive sheet of the present invention, even the surface tension of ground surpasses 40mN/m, after ultraviolet ray (UV) or electron beam (EB) irradiation, the bounding force at adhesive sheet and ground interface also reduces fully, it is good that the taking-up of semiconductor element becomes.Therefore, in the past,, on employed substrate film, carry out surface treatment, but adhesive sheet of the present invention there is no need to carry out the surface treatment of substrate film, thereby also be favourable on cost for the surface tension that makes ground is less than or equals 40mN/m.
Though abovely be described,, also can enumerate following adhesive sheet as a kind of mode of the best of adhesive sheet of the present invention about the present invention.
(the 12nd mode)
Preferred a kind of mode as adhesive sheet of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer contains: the weight-average molecular weight that contains the functional monomer of 10～400 parts by weight for more than or equal to 100,000 high molecular weight components, (b) 100 parts by weight thermopolymerization compositions and (c) 0.01～200 parts by weight produce the radioactive rays polymerizable compound of base compound by radiation exposure.
(the 13rd mode)
In addition, preferred a kind of mode as adhesive sheet of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is to contain: 100 parts by weight polyimide resins, (b) 1～200 parts by weight thermopolymerization composition and (c) 0.01～200 parts by weight produce the compound of base by radiation exposure.At this, in the above-mentioned the 12nd and 13 modes,,, preferably use Resins, epoxy and epoxy curing agent as the thermopolymerization composition from operation and stable on heating viewpoint.
(the 14th mode)
As a kind of mode of the present invention, can enumerate the adhesive sheet that possesses pressure sensitive adhesive layer and substrate layer, controls the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is above-mentioned pressure sensitive adhesive layer before (A2) radiation exposure adhesion strength during by 25 ℃ of  5.1mm probe assay for more than or equal to 0.5N, and (B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m.
(the 15th mode)
In addition, as a kind of mode of the present invention, can enumerate the adhesive sheet that possesses pressure sensitive adhesive layer and substrate layer, controls the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is above-mentioned pressure sensitive adhesive layer before (A2) radiation exposure adhesion strength during by 25 ℃ of  5.1mm probe assay for more than or equal to 0.5N, and (B2) melt viscosity during 160 ℃ before the radiation exposure is the adhesive sheet of 50～100000Pas.
(the 16th mode)
In addition, a kind of optimal way as adhesive sheet of the present invention, can enumerate the adhesive sheet that possesses pressure sensitive adhesive layer and substrate layer, controls the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is that the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after (C1) radiation exposure poor (bond strength behind the bond strength-radiation exposure before the radiation exposure) is more than or equal to 100mN/cm, and is to have the adhesive sheet that at least a characteristic in the following characteristic constitutes.
(D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, and the tan δ during behind the radiation exposure 180 ℃ is more than or equal to 0.1,
(D2) storage modulus during 120 ℃ before the radiation exposure is to be less than or equal to 10MPa, and the storage modulus during behind the radiation exposure 180 ℃ is to be less than or equal to 100MPa.
At this, viewpoint from the flowability that can control pressure sensitive adhesive layer, use has the adhesive sheet of characteristic (D1), have enough bounding forces during from lamination adhesive sheet on semiconductor wafer and when bonding semiconductor element, have enough fusible viewpoints, use adhesive sheet with characteristic (D2) in the temperature below 200 ℃.
(the 17th mode)
In addition, preferred a kind of mode as adhesive sheet of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, bond strength when above-mentioned pressure sensitive adhesive layer is 25 ℃ of pressure sensitive adhesive layer before and after (C2) radiation exposure poor (bond strengths during behind the bond strength-radiation exposure during before the radiation exposure 25 ℃ 25 ℃) is for more than or equal to 0.1N/  5.1mm probe, and is to have the adhesive sheet that at least a characteristic in the following characteristic constitutes.
(D1) the tan δ during 120 ℃ before the radiation exposure is more than or equal to 0.1, and the tan δ during behind the radiation exposure 180 ℃ is more than or equal to 0.1,
(D2) storage modulus during 120 ℃ before the radiation exposure is to be less than or equal to 10MPa, and the storage modulus during behind the radiation exposure 180 ℃ is to be less than or equal to 100MPa.
At this, viewpoint from the flowability that can control pressure sensitive adhesive layer, use has the adhesive sheet of characteristic (D1), have enough bounding forces during from lamination adhesive sheet on semiconductor wafer and when bonding semiconductor element, have enough fusible viewpoints, use adhesive sheet with characteristic (D2) in the temperature below 200 ℃.
(the 18th mode)
In addition, preferred a kind of mode as adhesive sheet of the present invention, be to possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, in above-mentioned adhesive sheet, the storage modulus of above-mentioned pressure sensitive adhesive layer under uncured or semi-cured state 50 ℃ is more than or equal to 0.1MPa, be less than or equal to 200MPa, the storage modulus of shining behind a certain amount of radioactive rays 50 ℃ is 2 times of pre-irradiation or more than it, and the above-mentioned pressure sensitive adhesive layer after having shone a certain amount of radioactive rays preferably has following (E), (F) and at least a characteristic in the characteristic (G) and the adhesive sheet that constitutes.
(E) amount of flow under 160 ℃ is more than or equal to 100 μ m, is less than or equal to 10000 μ m,
(F) melt viscosity under 160 ℃ is more than or equal to 50Pas, is less than or equal to 10 6Pas, and
(G) storage modulus under 180 ℃ is to be less than or equal to 100MPa.
(the 19th mode)
In addition, preferred a kind of mode as adhesive sheet of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, above-mentioned pressure sensitive adhesive layer is that the bond strength at above-mentioned pressure sensitive adhesive layer before (A1) radiation exposure and above-mentioned substrate layer interface is more than or equal to 200mN/cm and is to have at least a characteristic in the following characteristic and the adhesive sheet that constitutes.
(B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m,
(B2) melt viscosity during 160 ℃ before the radiation exposure is 50～100000Pas.
At this, from the viewpoint of cutting operation, use adhesive sheet with characteristic (B1), from fusible viewpoint, use adhesive sheet with (B2) characteristic.In addition, in above-mentioned adhesive sheet, the amount of flow before and after the radiation exposure than (irradiation back amount of flow/pre-irradiation amount of flow) preferably more than or equal to 0.1.In addition, in above-mentioned adhesive sheet, the bond strength before and after the radiation exposure at above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer interface preferably is less than or equal to 0.5 than (irradiation back bond strength/pre-irradiation bond strength).Have, in above-mentioned adhesive sheet, the bond strength before and after the radiation exposure at above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer interface poor (pre-irradiation bond strength-irradiation back bond strength) is preferably more than or equal to 100mN/cm again.And in above-mentioned adhesive sheet, the melt viscosity before and after the radiation exposure preferably is less than or equal to 100 than (irradiation back melt viscosity/pre-irradiation melt viscosity).
(the 20th mode)
Have again, preferred a kind of mode as adhesive sheet of the present invention, can enumerate and possess pressure sensitive adhesive layer and substrate layer, control the adhesive sheet of the bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer by the irradiation of radioactive rays, the storage modulus of above-mentioned pressure sensitive adhesive layer under uncured or semi-cured state 50 ℃ is more than or equal to 0.1MPa, be less than or equal to 200MPa, shone storage modulus under 50 ℃ behind a certain amount of radioactive rays and be 2 times of pre-irradiation or more than it, and, be that the above-mentioned pressure sensitive adhesive layer that has shone behind a certain amount of radioactive rays has at following (E), (F) and at least a characteristic in the characteristic (G) and the adhesive sheet that constitutes.
(E) amount of flow under 160 ℃ is more than or equal to 100 μ m, is less than or equal to 10000 μ m,
(F) melt viscosity under 160 ℃ is more than or equal to 50Pas, is less than or equal to 10 6Pas, and
(G) storage modulus under 180 ℃ is to be less than or equal to 100MPa.
In addition, in above-mentioned adhesive sheet, from obtaining good fusible viewpoint, the amount of flow B of the pressure sensitive adhesive layer after the pressure sensitive adhesive layer of the adhesive sheet of uncured or semi-cured state shines a certain amount of radioactive rays at the amount of flow A under 160 ℃ with to above-mentioned adhesive sheet preferably satisfies the relation of B/A 〉=1/10.In addition, the adhesive sheet of uncured or semi-cured state is shone the storage modulus of pressure sensitive adhesive layer under 50 ℃ behind a certain amount of radioactive rays preferably more than or equal to 15MPa.Have, above-mentioned pressure sensitive adhesive layer preferably satisfies following condition again.
1) storage modulus under uncured or semi-cured state 100 ℃ is more than or equal to 0.001MPa, is less than or equal to 2MPa, 2) storage modulus under 50 ℃ is more than or equal to 7.5MPa, is less than or equal to 50MPa, 3) behind the radiation exposure, storage modulus under 50 ℃ more than or equal to 15MPa, be less than or equal to 100MPa, 4) solidify the storage modulus of back under 50 ℃ more than or equal to 100MPa, be less than or equal to 5000MPa.Have again, use bond strength under 25 ℃ of lamination cured article of the square semiconductor element of 5mm of pressure sensitive adhesive layer of the adhesive sheet behind the radiation exposure and support member preferably more than or equal to the 3.0N/ sheet.Use Measurement of Dynamic Viscoelasticity device is measured the storage modulus of the pressure sensitive adhesive layer of the adhesive sheet after being heating and curing, and be more than or equal to 10MPa at 25 ℃, be less than or equal to 2000MPa, be more than or equal to 3MPa at 260 ℃, be less than or equal to 50MPa.
In addition, as other modes of the present invention, provide the manufacture method and the semiconductor device of following such semiconductor device.
Use adhesive sheet of the present invention, semiconductor element and mounting semiconductor element are mutually combined and the manufacture method of the semiconductor device that constitutes with support member or semiconductor element.
The manufacture method of semiconductor device comprises following operation: will have pressure sensitive adhesive layer and substrate layer and the adhesive sheet of the present invention that constitutes is attached to operation on the semiconductor wafer in the mode that above-mentioned pressure sensitive adhesive layer is sandwiched; Cut above-mentioned semiconductor wafer, form the operation of the semiconductor element that has pressure sensitive adhesive layer; The cutting back solidifies above-mentioned pressure sensitive adhesive layer to above-mentioned adhesive sheet irradiation radioactive rays, after this peels off the operation of above-mentioned substrate film layer; By above-mentioned adhesive sheet, the operation that support member that the semiconductor element that has above-mentioned pressure sensitive adhesive layer and mounting semiconductor element use or semiconductor element are mutually combined.
Use adhesive sheet of the present invention, semiconductor element and mounting semiconductor element are mutually combined with support member or semiconductor element and constitute semiconductor device.
Embodiment
Below, use embodiment to illustrate in greater detail the present invention.The present invention is not subjected to the restriction of these embodiment.Moreover, about the evaluation of adhesive sheet,, can carry out according to the method that illustrates in the evaluation method hurdle that illustrates afterwards as long as in each embodiment, do not specify.
(synthesis example 1) [synthesizing of light base propellant]
Use the electromagnetic type agitator to stir in room temperature, the 2-nitrobenzyl alcohol of 30g is dissolved in the 300g tetrahydrofuran (THF).In 30 minutes, in this solution, splash into be pre-mixed by 24.5g 4, the solution that 4 '-diphenylmethanediisocyanate and 100g tetrahydrofuran (THF) are formed was stirring at room 1 hour.After this, the Li Bixi cooling tube is installed, is carried out reaction in 2 hours while in oil bath, be heated to 60 ℃.After the reaction, be cooled to room temperature, use rotatory evaporator that reaction solution is concentrated into half.
In case resulting concentrated solution is added in the normal hexane of 1000 parts by weight, just obtains white depositions.This throw out of suction strainer 60 ℃ of one nights of drying, just obtains target product 2-nitre benzylamino carboxylic acid derivatives (PB-1) under vacuum.Output is 49.5g (yield 91%).
(synthesis example 2) [synthesizing of light base propellant]
In the trimethyl carbinol (15.0g), add to nitro rest in peace sour methyl esters (2.00g, 11mmol), N, N-dimethylhydrazine (0.66g, 11mmol), phenylglycidyl ether (1.66,11mmol), 50 ℃ stir 10 hours after, stirred 48 hours in room temperature (25 ℃) again, generate white precipitate.After filtering this white precipitate, carry out 2 times with ethyl acetate and clean, use the Vacuumdrier drying, obtain amine imide compound (PB-2).Output is 3.67g, and yield is 85%, and fusing point is 146-147 ℃.
(synthesis example 3) [synthesizing of light base propellant]
In the trimethyl carbinol (10g), add cyano group M-nitro benzoic acid methyl esters (2.00g, 12mmol), N, N-dimethylhydrazine (0.75g, 12mmol), phenylglycidyl ether (1.86,12mmol), 50 ℃ stir 72 hours after, again stirring at room 48 hours, after with the rotary evaporation moisture eliminator resulting reaction soln being removed the trimethyl carbinol, add the 10g ethyl acetate and carry out recrystallize, obtain the amine imide compound (PB-3) of white.Output is 2.74g, and yield is 65%, and fusing point is 148-149 ℃.
(synthesis example 4) [synthesizing of light base propellant]
Dissolving phenacyl bromide (2.00g in acetone (20g), 10.5mmol), to wherein adding 1 benzyl 2 methyl imidazole (1.73g, solution 10.5mmol) that is dissolved in the acetone (5g) at leisure, after this stirred 2 hours in room temperature (25 ℃), just separate out white crystals.Filter this white crystals, after carrying out cleaning for 2 times with acetone, under vacuum,, obtain imidazoles  bromide salt 1 (output 3.54g) 60 ℃ of dryings 5 hours.
The above-mentioned imidazolium bromide salt 1 of dissolving in methanol (15g/15g) solution (2.00g, 5.4mmol), to wherein adding sodium tetraphenylborate (1.84g, solution 5.4mmol) that is dissolved in the water (5.0g) at leisure.Along with interpolation, see separating out of white soup compound, after the interpolation, again stirring at room 5 hours.Filter precipitate, be dissolved in the acetone (20g) and carry out recrystallize, obtain the imidazoles  tetraphenyl borate salts (PB-4) (output 2.86g) of target.This compound shown in Figure 9 1The H-NMR spectrogram.In addition, fusing point and the thermolysis measured under the oxygen atmosphere with TG (thermogravimetric analysis)-DTA (differential thermal analysis) begin temperature, and its fusing point is 187 ℃, and kick off temperature is 224 ℃.
(synthesis example 5) [synthesizing of light base propellant]
(2.00g, 8.2mmol), (0.79g, solution 8.2mmol) after this stirring at room 2 hours, are separated out white crystals to dissolving p-nitrophenyl formyl monobromomethane in acetone (20g) to wherein adding the 1,2 dimethylimidazole that is dissolved in the acetone (5g) at leisure.Filter white crystals, after carrying out cleaning for 2 times with acetone, under vacuum,, obtain imidazoles  bromide salt 2 (output 2.62g) 60 ℃ of dryings 5 hours.
The above-mentioned imidazoles  bromide salt 2 of dissolving in methanol (15g/15g) solution (2.00g, 5.8mmol), to wherein adding sodium tetraphenylborate (2.01g, solution 5.8mmol) that is dissolved in the water (5.0g) at leisure.Along with interpolation, see separating out of white soup compound, after the interpolation, again stirring at room 5 hours.Filter precipitate, be dissolved in the acetone (20g) and carry out recrystallize, obtain the imidazoles  tetraphenyl borate salts (PB-5) (output 2.83g) of purpose.
This compound shown in Figure 10 1The H-NMR spectrogram.In addition, when beginning temperature with fusing point under the TG-DTA mensuration oxygen atmosphere and thermolysis, its fusing point is 165 ℃, and kick off temperature is 195 ℃.
(synthesis example 6) [synthesizing of polyimide resin]
In possessing the 500ml flask of thermometer, stirrer and calcium chloride tube, pack 2 into, two [4-(4-amino-benzene oxygen) phenyl] propane 41.05g (0.1mol) and the N-N-methyl-2-2-pyrrolidone N-150g of 2-, and stir.Behind two amine solvents, Yi Bian in ice bath, cool off flask, Yi Bian add 1 bit by bit, 10-(decamethylene) two (trimellitic acid 1,2-anhydride) 52.2g (0.1mol).After 3 hours, add 30g dimethylbenzene at room temperature reaction,, remove dimethylbenzene with the water azeotropic while be blown into nitrogen 150 ℃ of heating.This reaction solution is injected water, filter settled polymkeric substance, carry out drying, just obtain polyimide resin (PI-1).
(synthesis example 7) [synthesizing of polyimide resin]
In possessing the 500ml flask of thermometer, stirrer and calcium chloride tube, pack 1 into, 12-diamino dodecane 5.41g (0.045mol), ether diamine (BASF system, ether diamine 2000 (molecular weight: 1923)) 11.54g (0.01mol), polysiloxane diamine (the シ リ コ of SHIN-ETSU HANTOTAI-Application system, KF-8010 (molecular weight: 900)) 24.3g (0.045mol) and N-N-methyl-2-2-pyrrolidone N-169g, and stir.Behind two amine solvents, Yi Bian in ice bath, cool off flask, Yi Bian add (0.1mol) 4,4 '-(4,4 '-isopropylidene two phenoxy groups) two (O-phthalic acid dianhydrides) bit by bit) 31.23g.After 8 hours, add dimethylbenzene 112.7g at room temperature reaction,, remove dimethylbenzene with the water azeotropic while be blown into nitrogen 180 ℃ of heating.This reaction solution is injected water, filter settled polymkeric substance, drying obtains polyimide resin (PI-2).
(synthesis example 8) [synthesizing of polyimide resin]
The 41.0g (0.10mol) 2 that in the four-hole boiling flask of the 1L that possesses whipping appts, nitrogen ingress pipe and drying tube, packs into, two (4-(4-amino-benzene oxygen) phenyl) propane of 2-, adding the 250gN-N-methyl-2-2-pyrrolidone N-under nitrogen gas stream becomes solution.Flask is moved in the water-bath, Yi Bian carry out high degree of agitation, Yi Bian add 41.0g (0.10mol) 1 bit by bit, 2-(ethylidene) two (trimelitic dianhydride).Acid dianhydride roughly dissolves, and meanwhile or stir at leisure and reacted 6 hours, obtain polyamic acid solution.Then, in the four-hole boiling flask that adds above-mentioned polyamic acid solution, water distilling apparatus is installed, is added 220g dimethylbenzene.Under nitrogen gas stream, one side high degree of agitation in 180 ℃ oil bath, with the condensation water azeotropic that by imidization generate heat up in a steamer removal xylene on one side.This reaction soln is injected water, filter settled polymkeric substance, dry and obtain polyimide resin (PI-3).
In table 1, compile and represented resulting polyimide resin (composition and the rerum natura of PI-1～PI-3).Each rerum natura is measured by following condition.
(12)’Tg
Use differential scanning calorimeter (being designated hereinafter simply as DSC) (パ-キ Application エ Le マ-corporate system, DSC-7 type), under the condition of the heat-up rate of 10 ℃/min, measure.
(13) ' weight-average molecular weight
Measure with gel permeation chromatography (being designated hereinafter simply as GPC), convert according to polystyrene standard.
Table 1
Project PI-1 PI-2 PI-3
Form (mole) Diamines BAPP 0.1 - 0.1
DDO - 0.045 -
EDA - 0.01 -
KF-8010 - 0.045 -
DBTA 0.1 - -
Acid anhydrides BPADA - 0.1 -
EBTA - - 0.1
Rerum natura Tg(℃) 120 24 180
Weight-average molecular weight 120000 50000 150000
Mark in the table 1 is represented following material.
BAPP:2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-
DDO:1,12-diamino dodecane
FDA: ether diamine 2000 (molecular weight: 1923)
KF-8010: polysiloxane diamine (molecular weight: 900)
DBTA:1,10-(decamethylene) two (trimellitic acid 1,2-anhydrides)
BPADA:4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (O-phthalic acid dianhydrides)
FBTA:1,2-(ethylidene) two (trimelitic dianhydride)
Then, in Production Example 1～25, make adhesive sheet 1～25 with composition shown in table 2 and the table 3.The composition of adhesive sheet 1～25 compiles and is shown in table 2 and the table 3.
Table 2
Project Form (mass fraction)
Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Production Example 9 Production Example 10 Production Example 11 Production Example 12 Production Example 13
1 2 3 4 5 6 7 8 9 10 11 12 13
Resins, epoxy YOCN703 42.3 42.3 - - 42.3 42.3 42.3 42.3 42.3 42.3 42.3 42.3 42.3
EX-411 - - 76.0 - - - - - - - - - -
Ep828 - - - 45.0 - - - - - - - - -
ESCN195 - - - 15.0 - - - - - - - - -
Solidifying agent LF2882 23.9 23.9 39.0 40.0 23.9 23.9 23.9 23.9 23.9 23.9 23.9 23.9 23.9
Acrylic rubber HTR- 860P-3 44.1 44.1 76.7 66.7 44.1 44.1 44.1 44.1 44.1 44.1 44.1 44.1 44.1
Curing catalyst 2PZ-CN 0.4 0.4 0.5 0.5 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Coupling agent A-187 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7
Produce the compound of base by radiation exposure PB-1 0.5 - - - - - - - - 0.005 150 - -
I-369 - 0.5 1.0 0.8 - - - - - - - - -
PB-2 - - - - 0.5 0.5 - - - - - - -
PB-3 - - - - - - 0.5 - - - - - -
PB-4 - - - - - - - 0.5 - - - - -
PB-5 - - - - - - - - 0.5 - - - -
Sensitizing agent Benzophenone - - - - - 0.1 - - - - - - -
The optical polymerism composition 4G - - - - - - - - - - - - 22.05
1-184 - - - - - - - - - - - - 0.5
Table 3
Project Form (mass fraction)
Production Example 14 Production Example 15 Production Example 16 Production Example 17 Production Example 18 Production Example 19 Production Example 20 Production Example 21 Production Example 22 Production Example 23 Production Example 24 Production Example 25
14 15 16 17 18 19 20 21 22 23 24 25
Polyimide PI-1 50 50 50 50 50 50 50 50 50 50
PI-2 50
PI-3 50
Resins, epoxy ESCN-195 10 10 10 10 10 10 10 13 10 10 10 13
Solidifying agent H-1 5.3 5.3 5.3 5.3 5.3 5.3 5.3 6.9 5.3 5.3 5.3 6.9
Agent TPPK 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.13 0.2 0.2 0.2 0.13
Produce the compound of base by radiation exposure PB-1 0.2
I-369 0.2 4.0 0.004 120
PB-2 0.2 0.2
PB-3 0.2
PB-4 0.2
PB-5 0.2
Sensitizing agent Benzophenone 0.05
(Production Example 1)
By 42.3 parts by weight YDCN-703 (Toto Kasei KK's systems, trade(brand)name, the ortho-cresol linear epoxy resin, epoxy equivalent (weight) 210), 23.9 parts by weight phenolite resol LF2882 (big Japanese イ Application キ chemical industry Co., Ltd. system trade(brand)name, dihydroxyphenyl propane line style resin), 44.1 parts by weight HTR-860P-3 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, trade(brand)name, contain the epoxy group(ing) acrylic rubber, molecular weight 1,000,000, Tg-7 ℃), 0.4 parts by weight sulfuration colloidal sol 2PZ-CN (Shikoku Chem's system, trade(brand)name, 1-cyanoethyl-2-phenylimidazole), 0.7 parts by weight NUCA-187 (Japanese ユ ニ カ-Co., Ltd.'s system, trade(brand)name, γ-glycidoxypropyltrime,hoxysilane), 0.5 add methylethylketone in the composition that parts by weight 2-nitre benzylamino carboxylic acid derivatives (PB-1) is formed, mix, again vacuum outgas.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 140 ℃ of heat dryings 5 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 1) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, automatically static load) this adhesive sheet 1 is 170 ℃ of storage moduluss after solidifying 1 hour, and the result is to be 360MPa at 25 ℃, is 30MPa at 260 ℃.
(Production Example 2)
In Production Example 1, except 2-nitre benzylamino carboxylic acid derivatives (PB-1) changes 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system into, trade(brand)name: イ Le ガ キ ユ ア 369) in addition, carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 2) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, automatically static load) this adhesive sheet 2 is 170 ℃ of storage moduluss after solidifying 1 hour, and the result is to be 350MPa at 25 ℃, is 25MPa at 260 ℃.
(Production Example 3)
By 76.0 parts by weight Resins, epoxy (デ Na コ-Le, Denacol) EX-411 (Na ガ セ ケ system テ Star Network ス corporate system, trade(brand)name, aliphatic epoxy resin, 4 officials can, epoxy equivalent (weight) 231), 39.0 parts by weight phenolite resol LF2882 (big Japanese イ Application キ chemical industry Co., Ltd. system, trade(brand)name, dihydroxyphenyl propane line style resin), 76.7 parts by weight HTR-860P-3 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system trade(brand)name, contain the epoxy group(ing) acrylic rubber, molecular weight 1,000,000, Tg-7 ℃), 0.5 parts by weight sulfuration colloidal sol 2PZ-CN (Shikoku Chem's system trade(brand)name, 1-cyanoethyl-2-phenylimidazole), 0.7 parts by weight NUC A-187 (Japanese ユ ニ カ-Co., Ltd.'s system trade(brand)name, γ-glycidoxypropyltrime,hoxysilane), 1.0 parts by weight 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system, trade(brand)name: イ Le ガ キ ユ ア 369) add methylethylketone in the composition of Zu Chenging, mix, again vacuum outgas.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 140 ℃ of heat dryings 5 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 3) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 3 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 360MPa, is 10MPa at 260 ℃.
(Production Example 4)
By 45.0 parts by weight Ai Bikete Resins, epoxy 828 (ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd. system trade(brand)name, bisphenol A type epoxy resin, epoxy equivalent (weight) 190), 15.0 parts by weight ESCN195 (Sumitomo Chemical Company Ltd's trade(brand)name, the ortho-cresol linear epoxy resin, epoxy equivalent (weight) 195), 40.0 parts by weight プ ラ イ オ-Off エ Application LF2882 (big Japanese イ Application キ chemical industry Co., Ltd. system trade(brand)name, dihydroxyphenyl propane line style resin), 66.7 parts by weight HTR-860P-3 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system trade(brand)name, contain the epoxy group(ing) acrylic rubber, molecular weight 1,000,000, Tg-7 ℃), 0.5 parts by weight sulfuration colloidal sol 2PZ-CN (Shikoku Chem's system trade(brand)name, 1-cyanoethyl-2-phenylimidazole), 0.7 parts by weight NUC A-187 (Japanese ユ ニ カ-Co., Ltd.'s system trade(brand)name, γ-glycidoxypropyltrime,hoxysilane), 1.0 parts by weight 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system, trade(brand)name: イ Le ガ キ ユ ア 369) add methylethylketone in the composition of Zu Chenging, mix, again vacuum outgas.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 140 ℃ of heat dryings 5 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 4) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 4 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 360MPa, is 14MPa at 260 ℃.
(Production Example 5)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 being changed into amine imide compound (PB-2), carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 5) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 5 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 350MPa, is 35MPa at 260 ℃.
(Production Example 6)
Except in Production Example 1, adding 0.1 parts by weight benzophenone, carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 6) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 6 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 350MPa, is 35MPa at 260 ℃.
(Production Example 7)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 being changed into amine imide compound (PB-3), carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 7) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 7 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 350MPa, is 35MPa at 260 ℃.
(Production Example 8)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 being changed into imidazoles  tetraphenyl borate salts (PB-4), carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 8) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 8 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 340MPa, is 30MPa at 260 ℃.
(Production Example 9)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 being changed into imidazoles tetraphenyl borate salts (PB-5), carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 9) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 9 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 360MPa, is 35MPa at 260 ℃.
(Production Example 10)
Except the quantitative change with the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 is 0.005 parts by weight, carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 10) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 10 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 380MPa, is 30MPa at 260 ℃.
(Production Example 11)
Except the quantitative change with the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 1 is 150.0 parts by weight, carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 11) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 11 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 30MPa, is 1MPa at 260 ℃.
(Production Example 12)
In Production Example 1, except without the 2-nitre benzylamino carboxylic acid derivatives (PB-1), carry out and Production Example 1 identical operation, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 12) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 12 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 380MPa, is 30MPa at 260 ℃.
(Production Example 13)
By 42.3 parts by weight YDCN-703 (Toto Kasei KK's systems, trade(brand)name, the ortho-cresol linear epoxy resin, epoxy equivalent (weight) 210), 23.9 parts by weight phenolite resol LF2882 (big Japanese イ Application キ chemical industry Co., Ltd. system, trade(brand)name, dihydroxyphenyl propane line style resin), 44.1 parts by weight HTR-860P-3 (Na ガ セ ケ system テ Star Network ス Co., Ltd. system, trade(brand)name, contain the epoxy group(ing) acrylic rubber, molecular weight 1,000,000, Tg-7 ℃), 0.4 parts by weight sulfuration colloidal sol 2PZ-CN (Shikoku Chem's system, trade(brand)name, 1-cyanoethyl-2-phenylimidazole), 0.7 parts by weight NUC A-187 (Japanese ユ ニ カ-Co., Ltd.'s system, trade(brand)name, γ-glycidoxypropyltrime,hoxysilane), 22.05 parts by weight 4G (Xin Zhong village KCC system, trade(brand)name, dimethacrylate Tetraglycol 99 ester) and in the composition of 0.5 parts by weight 1-hydroxycyclohexylphenylketone composition add methylethylketone, mix, again vacuum outgas.This tackiness agent varnish of coating on the pet film of thick 50 μ m, 140 ℃ of heat dryings 5 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 13) of thickness 50 μ m of (pet film).
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) measure (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically) this adhesive sheet 13 is in the storage modulus of 170 ℃ of curing after 1 hour, and the result is, at 25 ℃ is 400MPa, is 50MPa at 260 ℃.
(Production Example 14)
Add the polyimide resin (PI-1) that 50 parts by weight obtain at 200 parts by weight in as the N-N-methyl-2-2-pyrrolidone N-of solvent in Production Example 6,10 parts by weight ortho-cresol linear epoxy resin (Nippon Kayaku K. K's systems, trade(brand)name: ESCN-195), 5.3g phenolic aldehyde line style resin is (bright and change into Co., Ltd.'s system, trade(brand)name: H-1), 0.2 (Co., Ltd.'s system, trade(brand)name: TPPK) are learned in northern Xinghua to parts by weight tetraphenylphosphonium  tetraphenyl borate salts (テ ト ラ Off エ ニ Le ホ シ ホ ニ ウ system テ ト ラ Off エ ニ Le ボ ラ ト), 0.2 the 2-nitre benzylamino carboxylic acid derivatives (PB-1) that parts by weight obtain in synthesis example 1 makes its dissolving.It is stirred well, carry out homodisperse, just obtain tackiness agent varnish.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 150 ℃ of heat dryings 20 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 14) of thickness 50 μ m of (pet film).
(Production Example 15)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 14 being changed into 2-benzyl-2-diaminomethyl-1-(4-morpholino phenyl)-1-butane-1-ketone (Ciba SpecialityChemicals corporate system, trade(brand)name: イ Le ガ キ ユ ア 369) in addition, carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 15) of thickness 50 μ m of (pet film).
(Production Example 16)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 14 being changed into amine imide compound (PB-2), carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 16) of thickness 50 μ m of (pet film).
(Production Example 17)
Except in Production Example 16, adding 0.05 parts by weight benzophenone, carry out and Production Example 16 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 17) of thickness 50 μ m of (pet film).
(Production Example 18)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 14 being changed into amine imide compound (PB-3), carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 18) of thickness 50 μ m of (pet film).
(Production Example 19)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 14 being changed into imidazoles  tetraborate (PB-4), carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 19) of thickness 50 μ m of (pet film).
(Production Example 20)
Except the 2-nitre benzylamino carboxylic acid derivatives (PB-1) in the Production Example 14 being changed into imidazoles  tetraborate (PB-5), carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 20) of thickness 50 μ m of (pet film).
(Production Example 21)
Add the polyimide resin (PI-2) that 50 parts by weight obtain at 200 parts by weight in as the N-N-methyl-2-2-pyrrolidone N-of solvent in Production Example 7,13 parts by weight ortho-cresol linear epoxy resin (Nippon Kayaku K. K's systems, trade(brand)name: ESCN-195), 6.9 parts by weight phenolic aldehyde line style resin is (bright and change into Co., Ltd.'s system, trade(brand)name: H-1), 0.13 (Co., Ltd.'s system is learned in northern Xinghua to parts by weight tetraphenylphosphonium  tetraphenyl borate salts, trade(brand)name: TPPK), 4.0 parts by weight 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system, trade(brand)name: イ Le ガ キ ユ ア 369) make its dissolving.It is stirred well, carry out homodisperse, obtain tackiness agent varnish.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 150 ℃ of heat dryings 20 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 21) of thickness 50 μ m of (pet film).
(Production Example 22)
In Production Example 15, except 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system, trade(brand)name: be beyond 0.004 parts by weight イ Le ガ キ ユ ア 369), carry out and Production Example 15 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 22) of thickness 50 μ m of (pet film).
(Production Example 23)
In Production Example 15, except 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (Ciba Speciality Chemicals corporate system, trade(brand)name: be beyond 120.0 parts by weight イ Le ガ キ ユ ア 369), carry out and Production Example 15 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 23) of thickness 50 μ m of (pet film).
(Production Example 24)
In Production Example 14, except not adding 2-nitre benzylamino carboxylic acid derivatives (PB-1), carry out and Production Example 14 identical operations, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 24) of thickness 50 μ m of (pet film).
(Production Example 25)
Add polyimide resin (PI-3), 13 parts by weight ortho-cresol linear epoxy resin (the Nippon Kayaku K. K's systems that 50 parts by weight obtain at 200 parts by weight in as the N-N-methyl-2-2-pyrrolidone N-of solvent in Production Example 8, trade(brand)name: ESCN-195), 6.9g phenolic aldehyde line style resin is (bright and change into Co., Ltd.'s system, trade(brand)name: H-1), (Co., Ltd.'s system, trade(brand)name: TPPK) make its dissolving are learned in northern Xinghua to 0.13 parts by weight tetraphenylphosphonium  tetraphenyl borate salts.It is stirred well, carry out homodisperse, obtain tackiness agent varnish.Polyethylene terephthalate (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system at thick 50 μ m, テ イ ジ Application テ ト ロ Application film: G2-50, surface tension 50 dynes per centimeter) go up this tackiness agent varnish of coating, 150 ℃ of heat dryings 20 minutes, make the possess ground adhesive sheet (thickness of the adhesive sheet except that ground is 50 μ m) (adhesive sheet 25) of thickness 50 μ m of (pet film).
About the adhesive sheet 1～25 that in Production Example 1～25, obtains, shown in following embodiment 1～45 and comparative example 1～11, estimate.
(embodiment 1～11)
The adhesive sheet 1～11 that use obtains in Production Example 1～11, make semiconductor element sample (forming the solder ball) in one side, this semiconductor element sample uses the wiring substrate of thick 25 μ m Kaptons to make with adhesive sheet laminated semiconductor chip with in ground, and thermotolerance and wet fastness are investigated.Stable on heating evaluation method is used the crackle of anti-reflowing property and temperature cycling test.The evaluation of anti-reflowing crackle, it is the IR reflowing stove that sample has been set by temperature, make the top temperature of sample surfaces reach 240 ℃ and kept 20 seconds in this temperature, with visual and ultrasonic microscope to repeatedly 2 times room temperature place and crackle in the sample of cooling process with peel off.With probability (%/100 chips) expression that crackle does not take place.Heatproof degree cyclicity, be in-55 ℃ atmosphere, to place 30 minutes with sample, the process of after this placing 30 minutes in 125 ℃ atmosphere is as 1 circulation, after through 1000 circulations, observes with ultrasonic microscope and not peel off or destructive probability (%/100 chips) expression such as crackle.In addition, the wet fastness evaluation is in 121 ℃ of temperature, humidity 100%, 2.03 * 10 5The atmosphere of Pa (pressure cooking test: PCT processing) was handled after 72 hours, peeled off by observation and carried out.With probability (%/100 chips) expression of not peeling off.
On the other hand, on the silicon wafer of thick 150 μ m, attach adhesive sheet 1～11, will be with the silicon wafer of adhesive sheet to be positioned on the cutting unit.Then, fixing semiconductor wafer on cutting unit, cut into 5mm * 5mm with the speed of 100mm/s after, use Co., Ltd.'s オ-Network to make made UV-330HQP-2 type exposure machine, with 500mJ/cm 2Exposure, expose from the supporting carrier film side of adhesive sheet, the sheet that will cut with withdrawing device takes out, fragment and taking-up property during to cutting are estimated.With when cutting chip the probability that disperses (%/100 chips) expression cutting the time chip disperse, with by taking out the small pieces combination, property is taken out in the probability that can take out the when chip after the cutting is taken out (%/100 slice) expression.
State on tape again on the silicon wafer of adhesive sheet with 500mJ/cm 2Exposure expose from the supporting carrier film side of adhesive sheet, measure the bond strength at the adhesive sheet/ground interface before and after (draw speed 50mm/min) exposure with 90 ° of stripping strengths.These evaluation results are compiled and are shown in Table 4.
(comparative example 1～2)
With the adhesive sheet 12 and 13 that in Production Example 12 and 13, obtains with embodiment 1 identical condition evaluating.The results are shown in the table 4.
(embodiment 12～21)
With the adhesive sheet 14～23 that in Production Example 14～23, obtains with embodiment 1 identical condition evaluating.The results are shown in the table 5.
(comparative example 3～4)
With the adhesive sheet 24 and 25 that in Production Example 24 and 25, obtains with embodiment 1 identical condition evaluating.The results are shown in the table 5.
Table 4
Project Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Comparative example 1 Comparative example 2
Adhesive sheet 1 2 3 4 5 6 7 8 9 10 11 12 13
Thermotolerance The crackle of anti-reflowing property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 75 (△) 100 (○) 0 (×)
The circulation of heatproof degree 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 75 (△) 100 (○) 0 (×)
Wet fastness 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 75 (△) 100 (○) 0 (×)
Chip during cutting disperses 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 20 (×) 0 (○)
Taking-up property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 50 (△) 100 (○) 0 (×) 100 (○)
90 ° of stripping strengths (mN/cm) After the exposure 4000 4000 4000 4000 4000 4000 4000 4000 4000 4000 350 180 4000
Before the exposure 80 65 80 75 75 65 70 75 70 100 80 180 60
Table 5
Project Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Comparative example 3 Comparative example 4
Adhesive sheet 14 15 16 17 18 19 20 21 22 23 24 25
Thermotolerance The crackle of anti-the reflowing 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 75 (△) 100 (○) 50 (△)
The circulation of heatproof degree 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 75 (△) 100 (○) 50 (△)
Wet fastness 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 50 (△) 100 (○) 50 (△)
Chip during cutting disperses 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 50 (×) 100 (×)
Taking-up property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 10 (△) 100 (○) 0 (×) -
Peel off (mN/cm) for 90 ° Before the exposure 4000 4000 4000 4000 4000 4000 4000 4000 4000 330 150 100
After the exposure 80 70 75 65 73 75 70 80 100 70 150 100
From table 4 and table 5 as can be known, adhesive sheet thermotolerance of the present invention and wet fastness are good, and the chip when also not cutting disperses, and taking-up property is also good.Because the bond strength difference before and after the exposure is big, so the operating condition handiness is big, operation is also good again.
(embodiment 22)
Be determined at adhesion strength, amount of flow and the melt viscosity of the radiation exposure front and back of the adhesive sheet of making in the Production Example 11 with following condition.Be shown in Table 6 in the lump with the above-mentioned table 4 and the evaluation result of table 5.
(10) ' adhesion strength
Use RHESCA corporate system Star キ Application グ trier, with the adhesion strengths of the method for putting down in writing among the JISZ0237-1991 at the pressure sensitive adhesive layer of 25 ℃ of above-mentioned adhesive sheets 1 of mensuration.Under following condition determination, record probe diameter  5.1mm, peeling rate 10mm/s, contact load 9.81 * 10 3Pa (100gf/cm 2), 1 second duration of contact.
(2) ' amount of flow
Above-mentioned adhesive sheet is cut into the size of 10 * 20mm, place it on the slide glass, make the pressure sensitive adhesive layer side adherence of adhesive sheet, use thermo-compressed testing apparatus (テ ス -Industry Co., Ltd's system), 160 ℃, with 0.8MPa pressurization 18 seconds, to the end of 4 samples, each sample is measured 2 points from the initial stage size to the longest distance of overflowing around with opticmicroscope from the lengthy motion picture of 20mm, amount to 8 mensuration, measure the amount of flow of forming by its mean value.
(3) ' melt viscosity
Pressure sensitive adhesive layer lamination with 8 above-mentioned adhesive sheets 1, after making the film of thick about 400 μ m, become the circle of diameter 11.3mm as test portion its stamping-out, at 160 ℃, with load 24.5N (2.5kgf) pressurization 5 seconds, use parallel flat plastometer method to measure, calculate melt viscosity (η) according to following formula.
t = η 3 V 2 8 πF [ 1 Z 4 - 1 ZO 4 ]
(in the formula, ZO represents the thickness of the adhesive film before the applied load, and Z represents the thickness of the adhesive film behind the applied load, and V represents the volume of adhesive film, and F represents the load that applies, and t represents the time of applied load.)
(embodiment 23～25)
With with adhesion strength, amount of flow and melt viscosity before and after embodiment 22 identical conditions are determined at the radiation exposure of the adhesive sheet of making in the Production Example 2～4 2～4.The results are shown in the table 6.
(embodiment 26～29)
With with adhesion strength, amount of flow and melt viscosity before and after embodiment 22 identical conditions are determined at the radiation exposure of the adhesive sheet of making in the Production Example 14～17 14～17.The results are shown in the table 6.
(comparative example 5～6)
With with adhesion strength, amount of flow and melt viscosity before and after embodiment 22 identical conditions are determined at the radiation exposure of the adhesive sheet 12 made in Production Example 12 and 25 and 25.The results are shown in the table 6.
Table 6
Project Embodiment 22 Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Comparative example 5 Comparative example 6
Adhesive sheet 1 2 3 4 14 15 16 17 12 25
90 ° of stripping strengths (m N/cm) Before the radiation exposure (A1) 4000 4000 4000 4000 4000 4000 4000 4000 180 100
Behind the radiation exposure 80 65 80 75 80 70 75 65 180 100
Radioactive rays are according to before the back/radiation exposure 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 1.00 1.00
Behind the radiation exposure-radioactive rays according to before 3920 3935 3920 3825 3920 3930 3925 3935 0 0
Adhesion strength (N) Before the radiation exposure (A2) 1.5 1.5 1.5 1.5 1.2 1.2 1.2 1.2 0.4 0.04
Behind the radiation exposure 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.4 0.04
Radioactive rays are according to before the back-radiation exposure 1.2 1.2 1.2 1.2 1.0 1.0 1.0 1.0 0 0
Amount of flow (μ m) Radioactive rays line pre-irradiation (B1) 1700 1800 2000 1800 1400 1600 1400 1400 500 80
Behind the radiation exposure 1200 1400 1200 1200 1150 1200 1100 1000 500 80
Radioactive rays are according to before the back/radiation exposure 0.67 0.75 0.56 0.63 0.79 0.71 0.75 0.67 1 1
Dissolve viscosity (Pas) Before the radiation exposure (B2) 90 80 75 80 105 110 100 100 50 40
Behind the radiation exposure 800 680 750 800 850 860 900 1100 50 40
Behind the radiation exposure/radiation exposure before 8.9 8.5 10.0 10.0 8.1 7.8 9.0 11.0 1.00 1.00
Thermotolerance The crackle of anti-reflowing property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 50 (△)
The circulation of heatproof degree 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 50 (△)
Wet fastness 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 50 (△)
Separation of fragments during cutting 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 20 (×) 100 (×)
Taking-up property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) -
As known from Table 6, therefore chip does not take place and disperses in the excellent in adhesiveness of the wafer before adhesive sheet of the present invention and the exposure when cutting.
In addition, the bond strength at the semi-conductor chip interface behind adhesive sheet of the present invention and the radiation exposure greatly reduces, and therefore taking-up property is good.
In addition, adhesive sheet of the present invention, because the mobile reduction of the film before and after the radiation exposure is few, so reliabilities such as thermotolerance, wet fastness are good.
(embodiment 30)
Use Co., Ltd.'s オ-Network to make made UV-330HQP-2 type exposure machine, with 500mJ/cm 2Exposure, the adhesive sheet of Production Example 1 being made from the substrate film side of adhesive sheet 1 is implemented the adhesion strength after exposure and embodiment 22 measure radiation exposure in the same manner.
In addition, on adhesive sheet 1, expose, use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4, static load automatically), according to tan δ and the storage modulus before and after the following condition mensuration radiation exposure with above-mentioned enforcement in the same manner.Be shown in Table 7 in the lump with the reliability evaluation result shown in table 4 and the table 5.
Specimen size: long 20mm, wide 4mm, thickness 80 μ m
Heat-up rate: 5 ℃/min
Mensuration mode: stretching mode
Frequency: 10Hz
(embodiment 31～33)
With with adhesion strength, tan δ and storage modulus before and after embodiment 30 identical conditions are determined at the radiation exposure of the adhesive sheet of making in the Production Example 2～4 2～4.Be shown in Table 7 in the lump with the reliability evaluation result shown in table 4 and the table 5.
(embodiment 34～37)
With with adhesion strength, tan δ and storage modulus before and after embodiment 30 identical conditions are determined at the radiation exposure of the adhesive sheet 14～16 made in Production Example 14～16 and 21 and 21.Be shown in Table 7 in the lump with the reliability evaluation result shown in table 4 and the table 5.
(comparative example 7～9)
With with adhesion strength, tan δ and storage modulus before and after embodiment 30 identical conditions are determined at the radiation exposure of the adhesive sheet 12,13 made in Production Example 12,13 and 25 and 25.Be shown in Table 7 in the lump with the reliability evaluation result shown in table 4 and the table 5.
Table 7
Project Embodiment 30 Embodiment 31 Embodiment 32 Embodiment 33 Embodiment 34 Embodiment 35 Embodiment 36 Embodiment 37 Comparative example 7 Comparative example 8 Comparative example 9
Adhesive sheet 1 2 3 4 14 15 16 21 12 13 25
90 ° of stripping strengths (mN/cm) Before the radiation exposure 4000 4000 4000 4000 4000 4000 4000 4000 180 4000 100
Behind the radiation exposure 80 65 80 75 80 70 75 80 180 60 100
Irradiation back-pre-irradiation (C1) 3920 3935 3920 3825 3920 3930 3925 3920 0 3935 0
Adhesion strength (N) Before the radiation exposure 1.5 1.5 1.5 1.5 1.2 1.2 1.2 1.2 0.4 1.4 0.04
Behind the radiation exposure 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.4 0.04 0.04
Irradiation back-pre-irradiation (C2) 1.2 1.2 1.2 1.2 1.0 1.0 1.0 1.0 0 1.36 0
tanδ (D1) Before the radiation exposure (120 ℃ 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.30 0.1
Behind the radiation exposure (180 ℃ 0.15 0.20 0.18 0.15 0.30 0.30 0.30 0.30 0.20 0.05 0.08
Storage modulus (MPa) (D2) Before the radiation exposure (120 ℃ 1.5 1.3 1.2 1.4 ≤0.01 ≤0.01 ≤0.01 ≤0.01 1.5 1 20
Behind the radiation exposure (180 ℃ 1.0 1.0 0.9 1.0 ≤0.01 ≤0.01 ≤0.01 ≤0.01 1.0 200 10
Thermotolerance The crackle of anti-reflowing property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) 50 (△)
The circulation of heatproof degree 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) 50 (△)
Wet fastness 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) 50 (△)
Taking-up property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) 100 (○) -
As known from Table 7, adhesive sheet of the present invention because behind radiation exposure and the bounding force of substrate film reduce fully, therefore taking-up property is good.Know that also because the reduction of its flowability is also few behind radiation exposure, so reliabilities such as thermotolerance, wet fastness are good.
(embodiment 38)
Use Co., Ltd.'s オ-Network to make made UV-330HQP-2 type exposure machine, with 500mJ/cm 2Exposure, from the substrate film side of adhesive sheet the adhesive sheet of making the Production Example 11 is implemented exposure, use and embodiment 30 identical devices are measured the storage modulus of radiation exposure front and back.In addition, 170 ℃ of storage moduluss of solidifying 1 hour pressure sensitive adhesive layer of mensuration too.On the other hand, measure the amount of flow behind the radiation exposure and dissolve viscosity according to similarly to Example 22 condition.Make semiconductor element sample (forming the solder ball) again in one side, this sample after with radiation exposure adhesive sheet laminated semiconductor chip (5mm * 5mm * 400 μ m) and in ground, use the wiring substrate of the Kapton of thick 25 μ m to make, use automatic bond testing machine shown in Figure 3 (Hitachi changes into テ Network Na プ ラ ト Application Co., Ltd. system), the bond strength under measuring 250 ℃.Be shown in Table 8 in the lump with the result shown in the table 2.
(embodiment 39～45)
With with storage modulus before and after embodiment 38 identical conditions are determined at the radiation exposure of the adhesive sheet 2～4 made in Production Example 2～4 and 14～17 and 14～17,170 ℃ of bond strengths of solidifying under the storage modulus of 1 hour pressure sensitive adhesive layer, amount of flow, melt viscosity behind the radiation exposure and 250 ℃.Be shown in Table 8 in the lump with the result shown in table 4 and the table 5.
(comparative example 10,11)
With with storage modulus before and after embodiment 38 identical conditions are determined at the radiation exposure of the adhesive sheet 12 made in Production Example 12 and 13 and 13,170 ℃ of bond strengths of solidifying under the storage modulus of 1 hour pressure sensitive adhesive layer, amount of flow, melt viscosity behind the radiation exposure and 250 ℃.Be shown in Table 8 in the lump with the result shown in table 4 and the table 5.
Table 8
Project Embodiment 38 Embodiment 39 Embodiment 40 Embodiment 41 Embodiment 42 Embodiment 43 Embodiment 44 Embodiment 45 Comparative example 10 Comparative example 11
Adhesive sheet 1 2 3 4 14 15 16 17 12 13
Storage modulus (MPa) Before the radiation exposure 50℃ 8 8 5 6 2 2 2 2 8 8
100℃ 0.8 0.8 0.5 0.7 0.01 0.01 0.01 0.01 0.8 0.8
Behind the radiation exposure 50℃ 25 20 15 18 15 15 15 16 8 200
180℃ (G) 1.0 1.0 0.9 1.0 ≤0.01 ≤0.01 ≤0.01 ≤0.01 1.0 200
After the curing 25℃ 360 350 300 320 200 200 200 220 380 400
50℃ 170 150 130 140 100 100 100 100 150 180
260℃ 30 25 10 14 8 8 8 9 30 50
Amount of flow behind the radiation exposure (160 ℃, μ m) (E) 1200 1400 1200 1200 1150 1200 1100 1000 500 60
Melt viscosity behind the radiation exposure (160 ℃, Pas) (F) 800 680 750 800 850 860 900 1100 50 40
Thermotolerance The crackle of anti-reflowing property 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×)
The circulation of heatproof degree 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×)
Wet fastness 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×)
Chip during cutting disperses 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 0 (○) 20 (×) 0 (○)
Extractable 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 100 (○) 0 (×) 100 (○)
Bond strength 250 ℃, N/ chip 10 10 8 9 8 8 8 8 1 0.05
As known from Table 8, adhesive sheet of the present invention, because the reduction of the flowability of film is few, so reliabilities such as thermotolerance, wet fastness are good before and after the radiation exposure.Know that in addition because the storage modulus difference before and after the radiation exposure is big, therefore chipless is dispersed when cutting, taking-up property is also good.
＜evaluation method 〉
(1) storage modulus
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4) storage modulus of mensuration adhesive sheet (specimen size: long 20mm, wide 4mm, thickness 80 μ m, 5 ℃/min of heat-up rate, stretching mode, 10Hz, static load automatically).
(2) mensuration of amount of flow
Be washed into rectangular of 1 * 2cm from the adhesive sheet of thick (thickness of the adhesive sheet except that ground) 50 μ m of possessing pressure sensitive adhesive layer and substrate layer (PET film (Supreme Being people デ ユ Port Application Off イ Le system Co., Ltd. system テ イ ジ Application テ ト ロ Application film)), be adjusted to the rectangle sample S of size 1 * 2cm.Then, in thermo-compressed testing apparatus (テ ス -Industry Co., Ltd's system), above-mentioned rectangle sample S is placed on the platform that is heated to 160 ℃, apply the pressure 18 seconds of 0.8MPa.After this, after from the thermo-compressed testing apparatus, taking out said sample S, as shown in figure 12, from the resin that overflow the end on the long limit (2cm limit) of said sample S, shown among the figure 55,56, (fore-and-aft distance a) in the 1st and the 2nd long distance of overflowing with light microscope determining.4 samples are carried out such operation, obtain the mean value that it overflows distance, promptly add up to 8 range averaging value, as amount of flow.
(3) melt viscosity
The melt viscosity of adhesive sheet uses according to parallel flat plastometer method and measures the value that calculates.8 adhesive sheets carry out lamination, make the film of thick about 400 μ m.This film is washed into the circle of diameter 11.3mm, as sample, at 160 ℃, adds compressive load 2.5kgf5 second, by the thickness of the sample before and after the pressurization, use formula 1 calculates melt viscosity.
t = η 3 V 2 8 πF [ 1 Z 4 - 1 ZO 4 ]
(in the formula, ZO represents the thickness of the adhesive film before the applied load, and Z represents the thickness of the adhesive film behind the applied load, and V represents the volume of adhesive film, and F represents the load that applies, and t represents the time of applied load.)
(4) to gold-plated stripping strength (bond strength)
On 120 ℃ hot plate, chip (5mm is square) and gold-plated substrate (band Copper Foil plated substrate electrolytic gold plating (Ni:5 μ m, Au:0.3 μ m)) are stacked on the adhesive sheet, carry out curing 130 ℃, 30 minutes and 170 ℃, 1 hour.This sample is measured the stripping strength under (85/85,48 hour) after normality and the moisture absorption 25 ℃.
(5) crackle of anti-reflowing property and heatproof degree cyclicity (test)
Use and make made UV-330HQP-2 type exposure machine, with 500mJ/cm with Co., Ltd.'s オ-Network 2The adhesive sheet that exposes from the supporting carrier film side of adhesive sheet of exposure, make semiconductor element sample (forming the solder ball) in one side, this sample is fitted the wiring substrate of the Kapton of semiconductor element and adhesive sheet and the thick 25 μ m of use and is made, and thermotolerance and wet fastness are investigated.Stable on heating evaluation method is applicable to the crackle of anti-reflowing property and the round-robin test of heatproof degree.The evaluation of the crackle of anti-reflowing property, be J-STD-020A according to the JEDEC standard, handle the semiconductor element sample of (85 ℃, 85% relative humidity, 168 hours) for the moisture absorption of having carried out being equivalent to grade 2, make it pass through the IR reflowing stove of design temperature, make the top temperature of specimen surface reach 265 ℃ and keeping more than 260 ℃ 10～20 seconds, with visual and ultrasonic microscope to placing and crackle in the sample of cooling process and peeling off in room temperature for 2 times repeatedly.Crackle not to take place as zero, with take place crackle as *.Heatproof degree cyclicity is to place 30 minutes in-55 ℃ atmosphere with sample, the process of after this placing 30 minutes in 125 ℃ atmosphere is as 1 circulation, after 1000 circulations, observe with ultrasonic microscope, with do not peel off or the destruction of crackle etc. as zero, with take place to destroy as *.
(6) wet fastness evaluation
In 121 ℃ of temperature, humidity 100%, 2.03 * 10 5The atmosphere of Pa (pressure cooking test: PCT processing) was handled after 72 hours, peeled off by observation and carried out the wet fastness evaluation.Do not peel off as zero to see, with peel off as *.
Chip when (7) cutting disperses and taking-up property
On the silicon wafer of thick 150 μ m, attach adhesive sheet, the silicon wafer of mounting band adhesive sheet on cutting unit.Then, fixing semiconductor wafer on cutting unit, cut into 5mm * 5mm with the speed of 100mm/s after, use Co., Ltd.'s オ-Network to make made UV-330HQP-2 type exposure machine, with 2000mJ/cm 2Exposure expose from the supporting carrier film side of adhesive sheet, use withdrawing device to take out the semiconductor element that has cut, the semiconductor element when cutting disperses and the evaluation of taking-up property.By taking out the small pieces combination, the probability that can take out (%/100 semiconductor elements) expression during with the semiconductor element after the taking-up cutting.
(8) storage modulus, tan δ
Use Measurement of Dynamic Viscoelasticity device (レ オ ロ ジ corporate system, DVE-V4, static load automatically), measure the storage modulus and the tan δ of pressure sensitive adhesive layer according to following condition.
Specimen size: long 20mm, wide 4mm, thickness 80 μ m
Heat-up rate: 5 ℃/min
Mensuration mode: stretching mode
Frequency: 10Hz
Peel off peeling force (bond strength) for (9) 90 °
In the mode that pressure sensitive adhesive layer is sandwiched, at 120 ℃ at semiconductor wafer superimposed layer adhesive sheet, to the silicon wafer of this band adhesive sheet, with 500mJ/cm 2Exposure from the ground side adhesive sheet is implemented exposure, measure (draw speed: the 50m/min) bond strength at the pressure sensitive adhesive layer/ground interface before and after the exposure with 90 ° of stripping strengths.
(10) adhesion strength
Use RHESCA corporate system adhesion ( Star キ Application グ) trier, according to the method for putting down in writing among the JISZ0237-1991, with following condition determination, the adhesion strength when measuring 25 ℃.
Probe diameter:  5.1mm, peeling rate: 10mm/s, contact load: 100gf/cm 2, duration of contact: 1s
(11) thermotolerance and wet fastness evaluation
Use Co., Ltd.'s オ-Network to make made UV-330HQP-2 type exposure machine, with 500mJ/cm 2The adhesive sheet that exposes from the supporting carrier film side of adhesive sheet of exposure, make semiconductor element sample (forming the solder ball) in one side, this sample is under 180 ℃, 0.4N, 5 seconds condition, with semiconductor element and adhesive sheet and in ground the wiring substrate of the Kapton of thick 25 μ m fit and make, thermotolerance and wet fastness are investigated.Stable on heating evaluation method is applicable to the crackle of anti-reflowing property and the round-robin test of heatproof degree.The evaluation of the crackle of anti-reflowing property is the benchmark according to the J-STD-020A of JEDEC standard, handle the semiconductor element sample of (85 ℃, 85% relative humidity, 168 hours) for the moisture absorption of having carried out being equivalent to grade 2, make it pass through the IR reflowing stove of design temperature, make the top temperature of specimen surface reach 265 ℃ and keeping more than 260 ℃ 10～20 seconds, with visual and ultrasonic microscope to placing and crackle in the sample of cooling process and peeling off in room temperature for 2 times repeatedly.So that crackle and peeling off as zero not to take place, with take place as *.Heatproof degree cyclicity is to place 30 minutes in-55 ℃ atmosphere with sample, the process of after this placing 30 minutes in 125 ℃ atmosphere is as 1 circulation, after 1000 circulations, observe with ultrasonic microscope, with do not peel off or the destruction of crackle etc. as zero, with take place to destroy as *.In addition, the wet fastness evaluation is in 121 ℃ of temperature, humidity 100%, 2.03 * 10 5The atmosphere of Pa (pressure cooking test: PCT processing) was handled after 72 hours, peeled off by observation and carried out.Do not peel off as zero to see, with peel off as *.
(12) Tg of the thermoplastic resin of Shi Yonging
Use differential scanning calorimeter (DSC), obtain the Tg of the thermoplastic resin of use with the condition of 10 ℃/min of heat-up rate.
(13) weight-average molecular weight of the thermoplastic resin of Shi Yonging
Use gel permeation chromatography to measure, convert with the polystyrene standard detection line.
(14) velocity of variation of the thermal value of obtaining by DSC
To this adhesive sheet, the irradiation of obtaining with DSC the thermal value of the pressure sensitive adhesive layer during radioactive rays as A, with respect to the velocity of variation (reactivity) during as B, calculate according to formula (B-A)/B with the thermal value before the radiation exposure.The DSC condition determination is as follows:
Heat-up rate: 10 ℃/min, mensuration temperature: 20 ℃～300 ℃
Peel off peeling force for (15) 90 °
Obtain, be with on the silicon wafer of adhesive sheet, at attaching adhesive sheet on the silicon wafer of thick 150 μ m with 500mJ/cm 2Exposure expose from the substrate film side, peel off peeling force with 90 ° and measure (draw speed: the 50mm/min) bond strength at the pressure sensitive adhesive layer/ground interface before and after the exposure.
The application is Japan's patent application of following same applicant formerly to propose, and is promptly special 2001-256285 number (the August 27 calendar year 2001 applying date), spy
Figure A20061010028700872
2001-256286 number (the August 27 calendar year 2001 applying date), spy 2001-262662 number (the August 31 calendar year 2001 applying date), spy
Figure A20061010028700874
2001-269013 number (September 5 calendar year 2001 applying date), spy 2002-35488 number (February 13 2002 applying date), spy 2002-37032 number (February 14 2002 applying date), spy 2002-76577 number (March 19 2002 applying date), spy
Figure A20061010028700878
2002-83777 number (March 25 2002 applying date), spy
Figure A20061010028700879
2002-83818 number (March 25 2002 applying date), spy 2002-83844 number (March 25 2002 applying date), spy
Figure A200610100287008711
The application of the right of priority in 2002-137252 number (May 13 2002 applying date) is introduced in this specification sheets as a reference at this specification sheets with these applications.
Applicability on the industry
Adhesive sheet of the present invention, can be as dicing tape in cutting process, in the engaging process of semiconductor element and support member, the adhesive good as joint reliability uses, in addition, in the occasion of mounting semiconductor element with the big semiconductor element of support member encapsulation coefficient of thermal expansion differences, it is to have necessary heat resistance, moisture-proof, and the good adhesive sheet of operation.
In addition, use the manufacture method of the semiconductor device of adhesive sheet of the present invention, can simplify manufacture process, and made semiconductor device has both necessary heat resistance, moisture-proof and operation in the occasion of mounting semiconductor element with the big semiconductor element of support member encapsulation coefficient of thermal expansion differences.

Claims (28)

1. adhesive sheet, the bounding force that this adhesive sheet has between pressure sensitive adhesive layer and substrate layer, above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, wherein, above-mentioned pressure sensitive adhesive layer is that the bond strength at preceding above-mentioned pressure sensitive adhesive layer of (A1) radiation exposure and above-mentioned substrate layer interface is more than or equal to 200mN/cm, and has at least one characteristic in the following characteristic:
(B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m
(B2) melt viscosity during 160 ℃ before the radiation exposure is 50～100000Pas.
2. adhesive sheet according to claim 1, wherein, in above-mentioned adhesive sheet, the amount of flow ratio before and after the radiation exposure, promptly the value of the amount of flow of postradiation amount of flow/pre-irradiation is more than or equal to 0.1.
3. adhesive sheet according to claim 1 and 2, wherein, in above-mentioned adhesive sheet, the bond strength ratio before and after the radiation exposure at above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer interface, promptly bond strength/value of pre-irradiation bond strength is to be less than or equal to 0.5 after the irradiation.
4. adhesive sheet according to claim 1 and 2, wherein, in above-mentioned adhesive sheet, the bond strength before and after the radiation exposure at above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer interface is poor, and the value of bond strength was more than or equal to 100mN/cm after promptly the pre-irradiation bond strength deducted and shines.
5. according to each described adhesive sheet in the claim 1～3, wherein, in above-mentioned adhesive sheet, the melt viscosity ratio before and after the radiation exposure, promptly melt viscosity/value of pre-irradiation melt viscosity is to be less than or equal to 100 in the irradiation back.
6. adhesive sheet, the bounding force that this adhesive sheet has between pressure sensitive adhesive layer and substrate layer, above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, above-mentioned pressure sensitive adhesive layer be before (A2) radiation exposure above-mentioned pressure sensitive adhesive layer by 25 ℃ of  5.1mm probe assay the time adhesion strength for more than or equal to 0.5N, and have at least one characteristic in the following characteristic:
(B1) amount of flow during 160 ℃ before the radiation exposure is 100～10000 μ m
(B2) melt viscosity during 160 ℃ before the radiation exposure is 50～100000Pas.
7. adhesive sheet according to claim 6, wherein, in above-mentioned adhesive sheet, the adhesion strength before and after the radiation exposure of above-mentioned pressure sensitive adhesive layer during by 25 ℃ of  5.1mm probe assay is poor, and promptly to deduct the value of irradiation back adhesion strength be more than or equal to 0.1N to the pre-irradiation adhesion strength.
8. according to claim 6 or 7 described adhesive sheets, wherein, in above-mentioned adhesive sheet, the amount of flow ratio before and after the radiation exposure, promptly the value of irradiation back amount of flow/pre-irradiation amount of flow is more than or equal to 0.1.
9. according to claim 6 or 7 described adhesive sheets, wherein, in above-mentioned adhesive sheet, the melt viscosity ratio before and after the radiation exposure, promptly melt viscosity/value of pre-irradiation melt viscosity is to be less than or equal to 100 in the irradiation back.
10. according to each described adhesive sheet in the claim 1～9, wherein, the bounding force between above-mentioned pressure sensitive adhesive layer and substrate layer is controlled by the irradiation radioactive rays.
11. adhesive sheet according to claim 10, wherein, above-mentioned radioactive rays are the light of wavelength 150nm～750nm.
12. according to each described adhesive sheet in the claim 1～11, wherein, the bond strength behind the radiation exposure is to be less than or equal to 100mN/cm.
13. adhesive sheet, the bounding force that this adhesive sheet has between pressure sensitive adhesive layer and substrate layer, above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, above-mentioned pressure sensitive adhesive layer is that the bond strength at the pressure sensitive adhesive layer/substrate layer interface before and after (C1) radiation exposure is poor, be bond strength before the radiation exposure value that deducts the bond strength behind the radiation exposure for more than or equal to 100mN/cm, and have at least one characteristic in the following characteristic:
Tan δ when (D1) the tan δ during 120 ℃ before and after the radiation exposure be more than or equal to 0.1, behind the radiation exposure 180 ℃ is more than or equal to 0.1,
Storage modulus when (D2) storage modulus during 120 ℃ before the radiation exposure is after being less than or equal to 10MPa, radiation exposure 180 ℃ is for being less than or equal to 100MPa.
14. adhesive sheet according to claim 13, wherein, in above-mentioned adhesive sheet, the bond strength ratio at the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, promptly the value of the bond strength before the bond strength/radiation exposure behind the radiation exposure is to be less than or equal to 0.5.
15. adhesive sheet according to claim 13, wherein, in above-mentioned adhesive sheet, the bond strength before the radiation exposure on the interface of pressure sensitive adhesive layer and substrate layer is more than or equal to 200mN/cm, and the above-mentioned bond strength behind the radiation exposure is to be less than or equal to 100mN/cm.
16. adhesive sheet, this adhesive sheet has pressure sensitive adhesive layer and substrate layer, bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, adhesion strength when above-mentioned pressure sensitive adhesive layer is 25 ℃ of pressure sensitive adhesive layer before and after (C2) radiation exposure is poor, the value of the adhesion strength the when adhesion strength when being 25 ℃ before the radiation exposure deducts behind the radiation exposure 25 ℃ is for more than or equal to 0.1N/  5.1mm probe, and has at least one characteristic in the following characteristic:
Tan δ when (D1) the tan δ during 120 ℃ before the radiation exposure be more than or equal to 0.1, behind the radiation exposure 180 ℃ is more than or equal to 0.1,
Storage modulus when (D2) storage modulus during 120 ℃ before the radiation exposure is after being less than or equal to 10MPa, radiation exposure 180 ℃ is for being less than or equal to 100MPa.
17. adhesive sheet according to claim 16, wherein, in above-mentioned adhesive sheet, the bond strength ratio at the pressure sensitive adhesive layer/substrate layer interface before and after the radiation exposure, promptly the value of the bond strength before the bond strength/radiation exposure behind the radiation exposure is to be less than or equal to 0.5.
18. adhesive sheet according to claim 17, wherein, in above-mentioned adhesive sheet, the bond strength before the radiation exposure on the interface of pressure sensitive adhesive layer and substrate layer is more than or equal to 200mN/cm, and the above-mentioned bond strength behind the radiation exposure is to be less than or equal to 100mN/cm.
19. adhesive sheet, this adhesive sheet has pressure sensitive adhesive layer and substrate layer, bounding force between above-mentioned pressure sensitive adhesive layer and above-mentioned substrate layer is controlled by radiation exposure, the storage modulus of above-mentioned pressure sensitive adhesive layer under uncured or semi-cured state 50 ℃ is more than or equal to 0.1MPa, is less than or equal to 200MPa, the storage modulus of shining under 50 ℃ behind a certain amount of radioactive rays is more than 2 times or 2 times of pre-irradiation, and have following (E), (F) and (G) shown in characteristic at least one characteristic:
(E) amount of flow under 160 ℃ for more than or equal to 100 μ m, be less than or equal to 10000 μ m,
(F) melt viscosity under 160 ℃ for more than or equal to 50Pas, be less than or equal to 106Pas, and
(G) storage modulus under 180 ℃ is for being less than or equal to 100MPa.
20. adhesive sheet according to claim 19, wherein, between the amount of flow B of the pressure sensitive adhesive layer after the pressure sensitive adhesive layer of the adhesive sheet of uncured or semi-cured state shines a certain amount of radioactive rays at the amount of flow A under 160 ℃ and to above-mentioned adhesive sheet, satisfy the relation of B/A 〉=1/10.
21. according to claim 19 or 20 described adhesive sheets, wherein, the storage modulus of the adhesive sheet of uncured or semi-cured state being shone under 50 ℃ of pressure sensitive adhesive layer behind a certain amount of radioactive rays is more than or equal to 15MPa.
22. according to each described adhesive sheet in the claim 19～21, pressure sensitive adhesive layer wherein meets the following conditions:
1) storage modulus under 100 ℃ of uncured or semi-cured state for more than or equal to 0.001MPa, be less than or equal to 2MPa,
2) storage modulus under 50 ℃ for more than or equal to 7.5MPa, be less than or equal to 50MPa,
3) behind the radiation exposure, the storage modulus under 50 ℃ for more than or equal to 15MPa, be less than or equal to 100MPa,
4) solidify after, 50 ℃ of storage moduluss down are more than or equal to 100MPa, are less than or equal to 5000MPa.
23. according to each described adhesive sheet in the claim 19～22, wherein, having used the bond strength under 250 ℃ of lamination cured article of the square semiconductor element of 5mm of pressure sensitive adhesive layer of the adhesive sheet behind the radiation exposure and support member is more than or equal to the 3.0N/ chip.
24. according to each described adhesive sheet in the claim 19～23, wherein, use the storage modulus of the pressure sensitive adhesive layer of the adhesive sheet after being heating and curing that the Measurement of Dynamic Viscoelasticity device measures to be more than or equal to 10MPa at 25 ℃, to be less than or equal to 2000Mpa, be more than or equal to 3MPa at 260 ℃, be less than or equal to 50MPa.
25. according to each described adhesive sheet in the claim 19～24, wherein, the bounding force between above-mentioned pressure sensitive adhesive layer and substrate layer is controlled by the irradiation radioactive rays.
26. adhesive sheet according to claim 25, wherein, above-mentioned radioactive rays are the light of wavelength 150nm～750nm.
27. according to each described adhesive sheet in the claim 19～26, wherein, the bond strength behind the radiation exposure is to be less than or equal to 100mN/cm.
28. the manufacture method of semiconductor device, this manufacture method has following operation:
To have each described pressure sensitive adhesive layer and substrate layer constitute in the claim 1～27 adhesive sheet and be attached to operation on the semiconductor wafer in the mode that above-mentioned pressure sensitive adhesive layer is sandwiched; Cut above-mentioned adhesive sheet and have the operation of the semiconductor element of pressure sensitive adhesive layer with formation; After cutting,,, peel off the operation of above-mentioned substrate film layer then so that above-mentioned pressure sensitive adhesive layer solidifies to above-mentioned adhesive sheet irradiation radioactive rays; Make the above-mentioned operation that the semiconductor element of pressure sensitive adhesive layer and support member that mounting semiconductor element is used or semiconductor element mutually combine that has by above-mentioned adhesive sheet.
29. semiconductor device, this semiconductor device have by using each described adhesive sheet in the claim 1～27, the structure that semiconductor element and mounting semiconductor element are mutually combined with support member or semiconductor element.
CN2006101002870A 2001-08-27 2002-08-27 Adhesive sheet and semiconductor device and process for producing the same Expired - Fee Related CN1916097B (en)

Applications Claiming Priority (32)

Application Number Priority Date Filing Date Title
JP2001256286 2001-08-27
JP2001-256285 2001-08-27
JP2001-256286 2001-08-27
JP2001256285 2001-08-27
JP2001256285 2001-08-27
JP2001256286 2001-08-27
JP2001262662 2001-08-31
JP2001262662 2001-08-31
JP2001-262662 2001-08-31
JP2001-269013 2001-09-05
JP2001269013 2001-09-05
JP2001269013 2001-09-05
JP2002035488 2002-02-13
JP2002-35488 2002-02-13
JP200235488 2002-02-13
JP2002037032 2002-02-14
JP2002-37032 2002-02-14
JP200237032 2002-02-14
JP2002076577 2002-03-19
JP200276577 2002-03-19
JP2002-76577 2002-03-19
JP2002083777 2002-03-25
JP200283844 2002-03-25
JP200283818 2002-03-25
JP200283777 2002-03-25
JP2002-83818 2002-03-25
JP2002-83844 2002-03-25
JP2002083818 2002-03-25
JP2002-83777 2002-03-25
JP2002083844 2002-03-25
JP2002-137252 2002-05-13
JP2002137252 2002-05-13

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CN102498548A (en) * 2009-07-09 2012-06-13 住友电木株式会社 Film for semiconductor and semiconductor device manufacturing method
CN103119663A (en) * 2010-09-28 2013-05-22 三菱制纸株式会社 Conductive material precursor and conductive material
CN103492433A (en) * 2011-02-14 2014-01-01 株式会社Lg化学 Solventless composition and method for preparing same
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CN102498548A (en) * 2009-07-09 2012-06-13 住友电木株式会社 Film for semiconductor and semiconductor device manufacturing method
CN103119663A (en) * 2010-09-28 2013-05-22 三菱制纸株式会社 Conductive material precursor and conductive material
CN103119663B (en) * 2010-09-28 2015-06-24 三菱制纸株式会社 Conductive material precursor and conductive material
CN103492433A (en) * 2011-02-14 2014-01-01 株式会社Lg化学 Solventless composition and method for preparing same
CN103492433B (en) * 2011-02-14 2016-12-14 株式会社Lg化学 solvent-free composition and preparation method thereof
CN105247661A (en) * 2013-05-29 2016-01-13 三井化学东赛璐株式会社 Adjustable mass resolving aperture
CN105247661B (en) * 2013-05-29 2018-09-21 三井化学东赛璐株式会社 The manufacturing method of semiconductor wafer protection film and semiconductor device
CN109715690A (en) * 2016-09-15 2019-05-03 日清纺控股株式会社 Resin combination and the thermal conductivity soft sheet material and radiator structure for using the resin combination
CN109715690B (en) * 2016-09-15 2021-06-25 日清纺控股株式会社 Resin composition, and heat conductive soft sheet and heat dissipation structure using same
US11225548B2 (en) 2016-09-15 2022-01-18 Nisshinbo Holdings Inc. Resin composition, heat-conductive flexible sheet using same, and heat dissipation structure

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